Triazine compounds, polymers comprising triazine structural units, and method

ABSTRACT

In various embodiments the present invention comprises 2,4,6-trisubstituted-1,3,5-triazine capping agents comprising one, two, or three leaving groups as substituents with any remaining substituents being essentially inert to reaction with a nucleophilic group on a polymer or monomer, or reactive with a nucleophilic group on a polymer or monomer at a slower rate than any leaving group. The invention also comprises polymers or monomers with nucleophilic groups capped with a triazine moiety. Still other embodiments of the invention comprise processes for capping nucleophilic groups in a polymer or monomer which comprises combining and reacting the polymer or monomer with a triazine-comprising capping agent.

CROSS REFERENCE TO RELATED APPLICATION

This application is a Divisional of U.S. patent application Ser. No.10/672,789 filed Sep. 26, 2003, which is a Continuation of U.S. patentapplication Ser. No. 09/941,050 filed Aug. 28, 2001, which is fullyincorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention is directed to triazine compounds, polymerscomprising triazine structural units, and methods for their preparation.More particularly, the present invention is directed to triazinecompounds capable of reacting with nucleophilic groups on polymers ormonomers; polymers which comprise at least one triazine moiety; andmethods for preparing the polymers.

Many polymers as synthesized contain nucleophilic end-groups ornucleophilic groups as pendant groups in the chain of the polymer, orboth. Nucleophilic end-groups may adversely affect the properties of thepolymers when the polymers are used in certain applications. Forexample, the presence of hydroxy end-groups in poly(arylene ether)s mayresult in decreased thermal stability. Similarly, the presence ofhydroxy end-groups in polycarbonates may result under certaincircumstances in poorer color or optical hue, high surface staticcharging, sticking, and dust attraction after injection molding, poorerheat and water resistance, and poorer heat aging resistance. Polymers inwhich nucleophilic end-groups, particularly hydroxy end-groups, havebeen capped may exhibit improved properties compared to thecorresponding polymers which have not been endcapped.

Capping of nucleophilic groups on polymers may be employed not only toimprove physical properties but also to introduce into the polymerreactive functionality different from the initial nucleophilic group.For example introduction of epoxy, orthoester, or olefinic functionalgroups through capping with appropriate epoxy-, orthoester-, or olefincomprising capping agents may provide reactive polymers which may beused in various applications such as copolymer formation forcompatibilization of immiscible polymer blends. Capping of nucleophilicgroups on polymers may also result in chain-extension or branching ofthe polymers if a difunctional or trifunctional capping agent is usedand more than one nucleophile-terminated chain participates in reaction.Also, capping of nucleophilic groups on polymers may result incross-linked polymers if the nucleophilic groups comprise pendant groupsand a difunctional or trifunctional capping agent is used.Chain-extended, branched, and cross-linked polymers often have improvedproperties such as increased melt strength for use in making blow moldedarticles.

Polymers endcapped through reaction with reactive triazine moieties havebeen reported. Nucleophile-terminated polymers such ashydroxy-terminated poly(arylene ether)s or hydroxy-terminatedpolycarbonates have been endcapped through reaction in solution withchlorotriazines as disclosed in U.S. Pat. Nos. 4,927,894, 5,034,527,5,115,043, 5,132,373, 5,210,191, and 5,264,496. Nucleophile-terminatedpolymers such as amine-terminated polysiloxanes have been endcappedthrough reaction in solution with chlorotriazines as disclosed in U.S.Pat. No. 5,324,796. Branching of hydroxy-terminated poly(arylene ether)susing trichlorotriazine (also known as cyanuric chloride) in a solutionreaction has been disclosed by White and Loucks in ACS Symposium Series,volume 282 (Reactive Oligomers), 187 (1985). Polycarbonates containingtriazine structural units in the chain and also branched polycarbonatesand molding compositions made therefrom have been disclosed in U.S. Pat.Nos. 3,957,728, 3,978,159, and 4,092,243. All of these referencesrequire that the incorporation of triazine structural units be carriedout in a solution reaction in the presence of a base. The subsequentrecovery of polymer typically requires antisolvent precipitation anddrying of recovered polymer. Methods must be provided for solventrecovery and disposal of any salt derived from the base. A method isneeded which provides a polymer with capped nucleophile groups in a meltprocess without the need for a base or recovery of large volumes ofsolvent.

Melt processes for endcapping of nucleophile-terminated polymers havebeen reported which rely on transesterification with a reactive ester.For example in U.S. Pat. No. 5,696,222 and in European PatentApplication EP 703,261 hydroxy-terminated polycarbonate is cappedthrough transesterification with a reactive ester. In one illustrativeprocess a bisphenol and diphenylcarbonate (DPC) are used as reactantsfor synthesis of a polycarbonate in a melt transesterification process.Endcapping of hydroxy end-groups to yield phenyl-capped end-groupsderived from DPC may be achieved by using a stoichiometric excess of DPCto give a desired endcap level and by driving the reaction equilibriumby applying a vacuum to remove the phenol byproduct. However, eitherexcess DPC must be used at the beginning of the reaction or additionalDPC must be added at a later reaction stage to compensate for theevaporative loss of the more volatile DPC reactant during later reactionstages at higher temperatures and pressures. Such use of excess DPC cangive a higher endcap level, but these off-stoichiometry conditionssacrifice reaction rate and molecular weight. In addition, late additionof DPC is limited in effectiveness because of DPC's volatility under thelater reaction conditions of higher temperature and lower pressure, andthe DPC lost in later reaction stages must be separated from the phenolbyproduct if they are to be recycled.

Another disadvantage is that the typical synthesis of a meltpolycarbonate from a bisphenol and a diarylcarbonate such as DPC offersonly the possibility of having unfunctionalized aryl end-groups on thepolymer unless other monophenols are added early in the reaction orunless a post-reaction process is used. Adding a monophenol can changethe end-group type, but may also adversely affect reaction rate andmolecular weight of the polymer. Also added monophenols may be volatileunder the reaction conditions. Also endcappers in post-reactionprocesses are often activated carbonates having a reactive leaving groupwhich must be prepared using the toxic chemical phosgene and thus arenot readily available at low cost.

A problem to be solved is to provide capping agents which are low cost,which react with nucleophile-containing monomers or withnucleophile-containing polymers during or subsequent to their synthesis,particularly in a melt process, and which release a species from thecapping agent which in one embodiment may be easily removed, such as bydevolatilization, and optionally recovered. In various embodiments it isalso desirable that a capping agent impart some property improvement toa polymer composition, for example through removal of residualnucleophilic groups such as hydroxy groups, or through the presence ofbeneficial substituents on a capping agent attached to a polymer. Inanother embodiment it is desirable that a capping agent be capable ofmodification to introduce functionality into a nucleophile-containingpolymer for subsequent reaction. In still another embodiment it isdesirable that a capping agent be capable of reacting with anucleophile-containing monomer as a participating species in apolymerization reaction. In still another embodiment it is desirablethat a capping agent be employable in a manner such as to allow apolymerization to be carried out rapidly at close to stoichiometricconditions until a desired molecular weight is achieved and then torapidly increase the endcap level and/or molecular weight to a desiredlevel by adding an endcapping agent. In still another embodiment it isdesirable that a capping agent be capable of modification to provide achain-extension, branching, or cross-linking agent. After diligentexperimentation the present inventors have discovered solutions to theseproblems.

SUMMARY OF THE INVENTION

In one embodiment the present invention comprises triazine-comprisingcapping agents of the formula (I):

wherein L¹ is an aryloxy group comprising at least one electronwithdrawing group ortho, meta, or para to the linkage between thearyloxy group and the triazine ring, and Z¹ and Z² are eachindependently groups which are essentially inert to reaction with anucleophilic group on a polymer or monomer, or which react with anucleophilic group on a polymer or monomer at a slower rate than thegroup, L¹.

In another embodiment the present invention comprisestriazine-comprising capping agents of the formula (II):

wherein L¹ and L² are each independently an aryloxy group comprising atleast one electron withdrawing group ortho, meta, or para to the linkagebetween the aryloxy group and the triazine ring, and Z¹ is a group whichis essentially inert to reaction with a nucleophilic group on a polymeror monomer, or which reacts with a nucleophilic group on a polymer ormonomer at a slower rate than either of the groups, L¹ and L².

In another embodiment the present invention comprisestriazine-comprising capping agents of the formula (III):

wherein L¹, L², and L³ are each independently an aryloxy groupcomprising at least one electron withdrawing group ortho, meta, or parato the linkage between the aryloxy group and the triazine ring.

Other embodiments of the invention comprise polymers with nucleophilicgroups capped with a triazine moiety. Still other embodiments of theinvention comprise processes for synthesizing polymers comprisingtriazine-comprising capping agents.

Various other features, aspects, and advantages of the present inventionwill become more apparent with reference to the following descriptionand appended claims.

DETAILED DESCRIPTION OF THE INVENTION

In the present context a polymer is a chemical species comprising atleast two monomer units. In the present context a triazine-comprisingcapping agent is a triazine compound comprising at least one ring carbonatom reactive to a nucleophilic group on a second chemical species. Insome embodiments a triazine-comprising capping agent is an endcappingagent. In one embodiment the present invention comprisestriazine-comprising compounds which are capable of reacting withnucleophilic groups on polymers or monomers through a displacementreaction or in an exchange reaction such as a transesterificationreaction or a transamidation reaction to provide reaction productscomprising a triazine-comprising polymer and at least one leaving groupderived from the triazine-comprising compound. In one embodiment thetriazine-comprising polymer is an end-capped polymer comprising at leastone triazine moiety as a terminal structural unit. Endcapped polymers inthe present context include those comprising at least onetriazine-comprising moiety as a terminal unit derived from reaction of anucleophile-containing polymer with a monofunctional triazine-comprisingcapping agent, or derived from reaction of a nucleophile-containingmonomer with a monofunctional triazine-comprising capping agent. Saidmonomer may be prereacted with monofunctional triazine-comprisingcapping agent in a separate reaction or may react with monofunctionaltriazine-comprising capping agent in the course of a polymerizationreaction.

In another embodiment triazine-comprising polymers include thosecomprising at least one triazine-comprising moiety as a structural unitin a polymer chain other than at a terminal site. Such structural unitsmay be derived from reaction of the nucleophile-containing polymer witha difunctional or with a trifunctional triazine-comprising cappingagent. In the latter two embodiments the resulting polymers may comprisecyclic polymers when a single polymer chain with two nucleophilicend-groups reacts with difunctional or with trifunctionaltriazine-comprising capping agent; or chain-extended or branchedpolymers, when more than one nucleophile-terminated polymer chain reactswith difunctional or with trifunctional triazine-comprising cappingagent, respectively. Triazine-comprising polymers which comprise atleast one triazine-comprising moiety as a structural unit in the polymerchain other than at a terminal site may also be derived from reaction ofa nucleophile-containing monomer with a difunctional or a trifunctionaltriazine-comprising capping agent. Said monomer may be prereacted withsuch a triazine-comprising capping agent in a separate reaction or mayreact with difunctional or trifunctional triazine-comprising cappingagent in the course of a polymerization reaction.

Triazine-comprising polymers in the present context also include thosecomprising both at least one triazine-comprising moiety as a terminalunit and at least one triazine-comprising moiety as a structural unit inthe polymer chain other than at a terminal site. In the present contexta monofunctional triazine-comprising capping agent is one which reactswith a nucleophilic group predominantly at only one reactive site on thetriazine ring; a difunctional triazine-comprising capping agent is onewhich reacts with a nucleophilic group predominantly at only tworeactive sites on the triazine ring; and a trifunctionaltriazine-comprising capping agent is one which reacts with anucleophilic group predominantly at three reactive sites on the triazinering.

Nucleophilic groups include those known in the art, illustrativeexamples of which are hydroxy, thiohydroxy, amino, and carboxy (orcarboxylate). In the present context the terms hydroxy and thiohydroxyinclude both aliphatic hydroxy or thiohydroxy groups and also aromatichydroxy or thiohydroxy groups (the latter of which are sometimesreferred to in the art as phenolic and thiophenolic groups,respectively).

Triazine-comprising compounds in various embodiments of the presentinvention include monofunctional triazine-comprising capping agentswhich are 2,4,6-trisubstituted-1,3,5-triazines of the formula (I):

wherein L¹ is a leaving group reactive with a nucleophilic group on apolymer or monomer, and Z¹ and Z² are each independently groups whichmay be essentially inert to reaction with a nucleophilic group on apolymer or monomer, or which may react with a nucleophilic group on apolymer or monomer at a slower rate than the leaving group, L¹. Invarious embodiments Z¹ and Z² are the same. In other embodiments Z¹ andZ² are essentially inert under the reaction conditions and do not reactwith a nucleophilic group on a polymer or monomer.

Triazine-comprising compounds in other embodiments of the presentinvention include difunctional triazine-comprising capping agents whichare 2,4,6-trisubstituted-1,3,5-triazines of the formula (II):

wherein L¹ and L² are each independently leaving groups reactive with anucleophilic group on a polymer or monomer, and Z¹ is a group which maybe essentially inert to reaction with a nucleophilic group on a polymeror monomer, or which may react with a nucleophilic group on a polymer ormonomer at a slower rate than either of the leaving groups, L¹ and L².In certain embodiments L¹ and L² are the same. In other embodiments Z¹is essentially inert under the reaction conditions and does not reactwith a nucleophilic group on a polymer or monomer.

Triazine-comprising compounds in other embodiments of the presentinvention include trifunctional triazine-comprising capping agents whichare 2,4,6-trisubstituted-1,3,5-triazines of the formula (III):

wherein L¹, L², and L³ are each independently leaving groups reactivewith a nucleophilic group on a polymer or monomer. In certainembodiments L¹, L², and L³ are the same.

In various embodiments L (as embodied in L¹, L², and L³) is halo, chloroor an aryloxy group comprising at least one electron withdrawing grouportho, meta, or para to the linkage between the aryloxy group and thetriazine ring. In one embodiment L is an aryloxy group comprising atleast one electron withdrawing group ortho or para to the linkagebetween the aryloxy group and the triazine ring. In another embodiment Lis an aryloxy group comprising at least one electron withdrawing grouportho or para to the linkage between the aryloxy group and the triazinering selected from the group consisting of carboalkoxy, carboaryloxy,carboaryl, halo, cyano, and nitro, and mixtures thereof. In anotherembodiment L is selected from the group consisting ofo-carbomethoxyphenoxy, o-carbomethoxymethylphenoxy,o-carboethoxyphenoxy, o-carbopropoxyphenoxy, o-chlorophenoxy,o-carbophenylphenoxy, o-carbophenoxyphenoxy, o-carbobenzoxyphenoxy, ando-nitrophenoxy.

In one embodiment leaving groups, L, are volatile and may be removedfrom a reaction mixture by devolatilization as leaving group compound.Removal of leaving group compound from a reaction mixture also serves todrive the equilibrium in favor of polymer or monomer comprising triazinestructural units. If desired, leaving group compound may be recoveredand recycled for further use. Leaving groups, L, may, if desired, alsohave substituents such as alkyl, aryl, alkaryl, aralkyl, alkoxy,aryloxy, silyl, halo, or fluoro substituents to assist in regulating themolecular weight and volatility of the triazine comprising compound orthe leaving group compound, or both. For example aryloxy groupscomprising at least one electron-withdrawing substituent may, ifdesired, also have substituents such as alkyl, aryl, alkaryl, aralkyl,alkoxy, aryloxy, silyl, halo, or fluoro substituents to assist inregulating the molecular weight and volatility of the triazinecomprising compound or the leaving group L, or both.

In various embodiments Z (as embodied in Z¹ and Z²) is at least one ofalkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy, alkylamino, or arylaminogroup, illustrative non-limiting examples of which include substitutedaryloxy, arylaryloxy, arylphenoxy, alkylphenoxy (for example,2-alkylphenoxy, 3-alkylphenoxy, and 4-alkylphenoxy), dialkylphenoxy (forexample, 2,6-dialkylphenoxy, 2,3-dialkylphenoxy, 2,5-dialkylphenoxy,2,4-dialkylphenoxy, 3,4-dialkylphenoxy, and 3,5-dialkylphenoxy),cyanophenoxy, halophenoxy, dihalophenoxy (for example,2,6-dihalophenoxy, 2,3-dihalophenoxy, 2,5-dihalophenoxy,2,4-dihalophenoxy, 3,4-dihalophenoxy, and 3,5-dihalophenoxy),2,6-dialkoxycarbonylphenoxy, trialkylphenoxy (for example,2,3,4-trialkylphenoxy, 2,3,5-trialkylphenoxy, 2,3,6-trialkylphenoxy,2,4,5-trialkylphenoxy, 3,4,5-trialkylphenoxy, and2,4,6-trialkylphenoxy), trihalophenoxy (for example,2,3,4-trihalophenoxy, 2,3,5-trihalophenoxy, 2,3,6-trihalophenoxy,2,4,5-trihalophenoxy, 3,4,5-trihalophenoxy, and 2,4,6-trihalophenoxy),and their tetra-substituted analogs. The aryloxy or arylamino groups maybe also be deactivated or rendered essentially inert towards reactionwith a nucleophilic group on a polymer or monomer by means ofelectron-donating groups, illustrative examples of which include alkoxy.Thus, in illustrative embodiments Z (as embodied in Z¹ and Z²) includesalkoxyphenoxy, dialkoxyphenoxy, and trialkoxyphenoxy. Other examples ofessentially inert groups suitable for Z may be found in U.S. Pat. No.5,696,222.

A triazine-comprising capping agent may also comprise a functionalitywhich is incorporated into a nucleophile-containing polymer or monomerwhen the polymer or monomer reacts with the triazine-comprising cappingagent. Illustrative triazine capping agents of this type are depicted informulas (IV)-(VI):

wherein L¹, L², and Z¹ are as defined above and Fu represents afunctional group which may be essentially inert to reaction or which mayreact with a nucleophilic group on a polymer or monomer at a slower ratethan a leaving group, L. In one embodiment of formula (V) each Fu groupis the same. In one embodiment of formula (VI) L¹ and L² are the same.Illustrative examples of functional groups, Fu, include vinyl, allyl,propargyloxy, and olefinic groups as illustrated by formula (VII; Fu¹),epoxy groups as illustrated by formula (VIII; Fu²), and cyclicorthoester groups as illustrated by formula (IX; Fu³):

wherein R¹ is alkyl or aryl; R² is hydrogen, alkyl, or aryl; Y¹ isnitrogen or oxygen; R³ is a C₁₋₆ alkylene radical, and R⁴ is a C₁₋₄primary or secondary alkyl radical or is an alkylene radical forming asecond 5- or 6-membered ring with C*, R⁵ is a C₁₋₄ primary or secondaryalkyl or C₆₋₁₀ aromatic radical, or R⁴ and R⁵ together with the atomsconnecting them form a 5-, 6-, or 7-membered ring; R⁶ is hydrogen or aC₁₋₄ primary or secondary alkyl; m is zero or one, and n is from 1 to2m; and x is zero when R⁴ and C* form a ring and is otherwise one.

In the context of the present invention alkyl radicals or groups arethose containing from 1 to about 30 carbon atoms, and include straightchain alkyl radicals, branched alkyl radicals and cycloalkyl radicals.Alkyl radicals may contain one or more unsaturated groups. Someillustrative non-limiting examples of alkyl radicals include methyl,ethyl, propyl, isopropyl, allyl, butyl, tertiary-butyl, pentyl,neopentyl, hexyl, hexenyl, octyl, nonyl, decyl, dodecyl, dodecenyl,pentadecyl, pentadecenyl, hexadecyl, octadecyl, oleyl, lauryl, palmityl,and stearyl. Cycloalkyl radicals or groups are typically thosecontaining from 3 to about 12 ring carbon atoms. Some illustrativenon-limiting examples of cycloalkyl radicals include cyclobutyl,cyclopentyl, cyclohexyl, methylcyclohexyl, and cycloheptyl. Alkylaminoradicals include those of the formula R¹R²N— wherein R¹ and R² are eachindependently an alkyl group as defined above, or wherein R¹ and R² arepart of a heterocyclic ring system, illustrative examples of whichinclude pyrrolidyl, piperidyl, and morpholinyl. Aryl radicals or groups(and consequently arylamino and aryloxy groups) in the present contextmay be either substituted or unsubstituted, and are typically all-carbonring systems or heteroaromatic ring systems containing from 4 to 14 ringcarbon atoms. Some illustrative non-limiting examples of aryl radicalsinclude furyl, chromanyl, phenyl, biphenyl, naphthyl, and anthranyl.Substituted aryl radicals are not limited as to position of substitutionprovided that a triazine-comprising moiety comprising the substitutedaryl radical can be prepared. Thus, in the case of phenyl radicals (andconsequently phenylamino and phenoxy groups) a substituent may be in theortho, meta, or para position. Typical aralkyl and alkaryl radicals orgroups are those containing from 7 to about 24 carbon atoms. Theseinclude, but are not limited to, benzyl, ethylphenyl, phenylbutyl,phenylpropyl, propylphenyl, and phenylethyl. In illustrative embodimentsof the invention R¹ is methylene and R² is hydrogen wherein Fu¹ isderived from allyl alcohol; R¹ is phenyl and R² is hydrogen wherein Fu¹is derived from 4-hydroxystyrene; R¹ is ethylene and R² is phenylwherein Fu¹ is derived from cinnamyl alcohol; R¹ is phenyl-2-methyleneor phenyl-4-methylene and R² is hydrogen wherein Fu¹ is derived from 2-or 4-allylphenol, respectively; or R¹ is 2-methoxyphenyl-4-methylene andR2 is hydrogen wherein Fu¹ is derived from eugenol. In other embodimentsof the invention R¹ is methylene wherein Fu² is derived from glycidol.In other embodiments of the invention R³ is methylene, ethylene,propylene, tetramethylene, pentamethylene, or hexamethylene; and R⁴ ismethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or sec-butyl. Invarious embodiments the cyclic orthoester moiety is a five membered ringin which m is zero and n is one; or a six-membered ring in which eitherm and n are both one, or m is zero and n is two. Illustrative examplesof cyclic orthoester moieties of formula (IX) include those of formulas(X) and (XI):

Formula (X) is the 4-(2-methoxy-2-methyl-1,3-dioxolanyl) radical. In oneembodiment said radical may be derived from4-hydroxymethyl-2-methoxy-2-methyl-1,3-dioxolane (and is hereinaftersometimes referred to as 4-oxymethyl-2-methoxy-2-methyl-1,3-dioxolaneradical) which is obtainable by the reaction of glycerol and methylorthoacetate. Formula (XI) is the4-(1-methyl-2,6,7-trioxabicyclo[2.2.2]octyl) radical and in oneembodiment the methylol derivative may be prepared by the reaction ofethyl orthoacetate with pentaerythritol.

Illustrative, non-limiting embodiments of monofunctionaltriazine-comprising capping agents include compounds of the formula (I)in which L¹ is selected from the group consisting of chloro,o-carbomethoxyphenoxy, o-carbomethoxymethylphenoxy,o-carboethoxyphenoxy, o-carbopropoxyphenoxy, o-chlorophenoxy,o-carbophenylphenoxy, o-carbophenoxyphenoxy, o-carbobenzoxyphenoxy, ando-nitrophenoxy; and Z¹ and Z² are each independently selected from thegroup consisting of methyl, phenyl, methoxy, ethoxy, isopropoxy,n-butoxy, iso-butoxy, t-butoxy, benzyloxy, cyclohexyloxy,methylcyclohexyloxy, nonyloxy, decyloxy, octadecyloxy, oleyloxy,phenoxy, n-butylphenoxy, isobutylphenoxy, t-butylphenoxy,4-t-butylphenoxy, n-pentylphenoxy, 4-t-amylphenoxy, n-hexylphenoxy,cyclohexylphenoxy, 4-cumylphenoxy, 4-(1,1,3,3-tetramethylbutyl)phenoxy,octylphenoxy, 4-tert-octylphenoxy, nonylphenoxy, dodecylphenoxy,octadecylphenoxy, pentadecylphenoxy, pentadecenylphenoxy,2-methoxyethylphenoxy, 4-(4′-oxyphenyl)-2,2,4-trimethylchroman,2-(4′-oxyphenyl)-2,4,4-trimethyl chroman,1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene,phenylphenoxy, naphthylphenoxy,1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene,4-cyanophenoxy, 4-halophenoxy, 4-bromophenoxy, methoxyphenoxy,phenoxyphenoxy, benzyloxyphenoxy, n-hexyloxyphenoxy, dimethoxyphenoxy,2,6-dimethylphenoxy, 2,6-di-t-butylphenoxy, 3,5-di-t-butylphenoxy,3,5-dicumylphenoxy, 2,4-di-t-butylphenoxy, 2,5-di-t-butylphenoxy,2,5-dicumylphenoxy, 2,3-di-t-butylphenoxy, dibromophenoxy,2,6-dibromophenoxy, 2,6-dichlorophenoxy, 2,6-(dimethoxycarbonyl)phenoxy,2,3,6-trimethylphenoxy, 2,4,6-trimethylphenoxy, tribromophenoxy,2,4,6-tribromophenoxy, and 2,4,6-trichlorophenoxy.

The radicals 4-(4′-oxyphenyl)-2,2,4-trimethylchroman and2-(4′-oxyphenyl)-2,4,4-trimethylchroman are derived from compounds (XII)and (XIII), respectively:

The radicals1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzeneand1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)benzeneare derived from compounds (XIV) and (XV), respectively:

Illustrative embodiments of monofunctional triazine-comprising cappingagents also include compounds of the formulas (IV) and (V) in which L¹is selected from the group consisting of chloro, o-carbomethoxyphenoxy,o-carbomethoxymethylphenoxy, o-carboethoxyphenoxy,o-carbopropoxyphenoxy, o-chlorophenoxy, o-carbophenylphenoxy,o-carbophenoxyphenoxy, o-carbobenzoxyphenoxy, and o-nitrophenoxy; Z¹, ifpresent, is selected from the group consisting of methyl, phenyl,methoxy, ethoxy, isopropoxy, n-butoxy, iso-butoxy, t-butoxy, benzyloxy,cyclohexyloxy, methylcyclohexyloxy, nonyloxy, decyloxy, octadecyloxy,oleyloxy, phenoxy, n-butylphenoxy, isobutylphenoxy, t-butylphenoxy,4-t-butylphenoxy, n-pentylphenoxy, 4-t-amylphenoxy, n-hexylphenoxy,cyclohexylphenoxy, 4-cumylphenoxy, 4-(1,1,3,3-tetramethylbutyl)phenoxy,octylphenoxy, 4-tert-octylphenoxy, nonylphenoxy, dodecylphenoxy,octadecylphenoxy, pentadecylphenoxy, pentadecenylphenoxy,2-methoxyethylphenoxy, 4-(4′-oxyphenyl)-2,2,4-trimethylchroman,2-(4′-oxyphenyl)-2,4,4-trimethylchroman,1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene,phenylphenoxy, naphthylphenoxy,1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene,4-cyanophenoxy, 4-halophenoxy, 4-bromophenoxy, methoxyphenoxy,phenoxyphenoxy, benzyloxyphenoxy, n-hexyloxyphenoxy, dimethoxyphenoxy,2,6-dimethylphenoxy, 2,6-di-t-butylphenoxy, 3,5-di-t-butylphenoxy,3,5-dicumylphenoxy, 2,4-di-t-butylphenoxy, 2,5-di-t-butylphenoxy,2,5-dicumylphenoxy, 2,3-di-t-butylphenoxy, dibromophenoxy,2,6-dibromophenoxy, 2,6-dichlorophenoxy, 2,6-(dimethoxycarbonyl)phenoxy,2,3,6-trimethylphenoxy, 2,4,6-trimethylphenoxy, tribromophenoxy,2,4,6-tribromophenoxy, and 2,4,6-trichlorophenoxy; and Fu is selectedfrom the group consisting of vinyl, allyl, allyloxy, 2-allylphenoxy,4-allylphenoxy, 4-ethenylphenoxy, cinnamyloxy, 4-allyl-2-methoxyphenoxy,propargyloxy, glycidoxy, and4-(2-methoxy-2-methyl-1,3-dioxolanyl)methoxy4-oxymethyl-2-methoxy-2-methyl-1,3-dioxolane.

Illustrative embodiments of difunctional triazine-comprising cappingagents include compounds of the formula (II) in which L¹ and L² are eachindependently selected from the group consisting ofo-carbomethoxyphenoxy, o-carbomethoxymethylphenoxy,o-carboethoxyphenoxy, o-carbopropoxyphenoxy, o-chlorophenoxy,o-carbophenylphenoxy, o-carbophenoxyphenoxy, o-carbobenzoxyphenoxy, ando-nitrophenoxy; and Z¹ is selected from the group consisting of methyl,phenyl, methoxy, ethoxy, isopropoxy, n-butoxy, iso-butoxy, t-butoxy,benzyloxy, cyclohexyloxy, methylcyclohexyloxy, nonyloxy, decyloxy,octadecyloxy, oleyloxy, phenoxy, n-butylphenoxy, isobutylphenoxy,t-butylphenoxy, 4-t-butylphenoxy, n-pentylphenoxy, 4-t-amylphenoxy,n-hexylphenoxy, cyclohexylphenoxy, 4-cumylphenoxy,4-(1,1,3,3-tetramethylbutyl)phenoxy, octylphenoxy, 4-tert-octylphenoxy,nonylphenoxy, dodecylphenoxy, octadecylphenoxy, pentadecylphenoxy,pentadecenylphenoxy, 2-methoxyethylphenoxy,4-(4′-oxyphenyl)-2,2,4-trimethylchroman,2-(4′-oxyphenyl)-2,4,4-trimethylchroman,1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene,phenylphenoxy, naphthylphenoxy,1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene,4-cyanophenoxy, 4-halophenoxy, 4-bromophenoxy, methoxyphenoxy,phenoxyphenoxy, benzyloxyphenoxy, n-hexyloxyphenoxy, dimethoxyphenoxy,2,6-dimethylphenoxy, 2,6-di-t-butylphenoxy, 3,5-di-t-butylphenoxy,3,5-dicumylphenoxy, 2,4-di-t-butylphenoxy, 2,5-di-t-butylphenoxy,2,5-dicumylphenoxy, 2,3-di-t-butylphenoxy, dibromophenoxy,2,6-dibromophenoxy, 2,6-dichlorophenoxy, 2,6-(dimethoxycarbonyl)phenoxy,2,3,6-trimethylphenoxy, 2,4,6-trimethylphenoxy, tribromophenoxy,2,4,6-tribromophenoxy, and 2,4,6-trichlorophenoxy. Illustrativeembodiments of difunctional triazine-comprising capping agents alsoinclude compounds of the formula (VI) in which L¹ and L² are eachindependently selected from the group consisting of chloro,o-carbomethoxyphenoxy, o-carbomethoxymethylphenoxy,o-carboethoxyphenoxy, o-carbopropoxyphenoxy, o-chlorophenoxy,o-carbophenylphenoxy, o-carbophenoxyphenoxy, o-carbobenzoxyphenoxy, ando-nitrophenoxy; and Fu is selected from the group consisting of vinyl,allyl, allyloxy, 2-allylphenoxy, 4-allylphenoxy, 4-ethenylphenoxy,cinnamyloxy, 4-allyl-2-methoxyphenoxy, propargyloxy, glycidoxy, and4-oxymethyl-2-methoxy-2-methyl-1,3-dioxolane.

Illustrative embodiments of trifunctional triazine-comprising cappingagents include compounds of the formula (III) in which L¹, L², and L³are each independently selected from the group consisting ofo-carbomethoxyphenoxy, o-carbomethoxymethylphenoxy,o-carboethoxyphenoxy, o-carbopropoxyphenoxy, o-chlorophenoxy,o-carbophenylphenoxy, o-carbophenoxyphenoxy, o-carbobenzoxyphenoxy, ando-nitrophenoxy. In one embodiment L¹, L², and L³ are each2-carbomethoxyphenoxy.

Methods of making triazine-comprising compounds of the present inventioninclude those methods known in the art. In various embodiments cyanuricchloride (2,4,6-trichloro-1,3,5-triazine) is contacted under reactiveconditions with precursors for Z (if present), Fu (if present), and L.In one embodiment the precursors are contacted with cyanuric chloridesequentially in the order: Z, followed by Fu, followed by L. In anotherembodiment the precursors are contacted with cyanuric chloridesequentially in the order: Fu, followed by Z, followed by L. In anotherembodiment the precursors are contacted with cyanuric chloridesequentially in the order: Z, followed by L. Examples of precursorsinclude derivatives of alcohols, amines, phenols, and anilines. Reactiveconditions generally comprise the presence of a solvent and anacid-acceptor for hydrochloric acid which is typically released uponreaction of cyanuric chloride with precursor compounds. In oneembodiment the acid-acceptor comprises aqueous sodium hydroxide and thereaction is carried out in a two-phase mixture of water and organicsolvent, in which case a phase transfer catalyst may optionally bepresent. Phase transfer catalysts are well-known in the art and includequaternary ammonium and phosphonium compounds. In another embodiment theacid acceptor comprises a tertiary amine. In another embodiment theacid-acceptor comprises sodium hydride and the reaction is carried outin an organic solvent. In various embodiments a process step is includedfor separation of salt.

Nucleophile-containing polymers of the present invention comprise allthose known in the art capable of being processed under solution, melt,or slurry conditions, such as, but not limited to,nucleophile-containing thermoplastic, thermoplastic-elastomeric, orelastomeric resins, or oligomers. Illustrative examples include, but arenot limited to, nucleophile-terminated polyethers, poly(arylene ether)s,poly(phenylene ether)s, poly(2,6-dimethylphenylene ether)s,polyethersulfones, polyetheresters, polyetherimides, polyamideimides,polyimides, polyetherketones, polyaryletherketones,polyetheretherketones, polyetherketoneketones, poly(arylene sulfide)s,poly(phenylene sulfide)s, polyacetals, polycarbonates, polyesters,poly(alkylene terephthalate)s, polyarylates, liquid crystallinepolyesters, polyestercarbonates, polysulfones, polyethylene glycols,polypropylene glycols, polyethylene-propylene glycols, oxidizedpolyolefins, siloxanes, amine-terminated siloxanes, andhydroxy-terminated siloxanes such as eugenol-capped siloxanes.Illustrative examples also include polymers with nucleophilic groupspendant in the polymer chain such as hydroxy-containing siloxanes,amine-containing siloxanes, copolymers containing hydroxyalkylacrylates,oxidized polyolefins, and phenoxy resins. Nucleophile-containingmonomers in the present context comprise those suitable for makingnucleophile-containing polymers of the present invention. In variousembodiments nucleophile-containing monomers of the present inventioncomprise those which may participate in a condensation polymerizationreaction to make nucleophile-containing polymers of the presentinvention.

In one embodiment the present invention comprises poly(phenylene ether)swhich comprise triazine structural units. Poly(phenylene ether)s(sometimes referred to hereinafter as “PPE”) are known polymerscomprising a plurality of structural units of the formula (XVI):

wherein in each of said units independently, each Q¹ is independentlyhalogen, primary or secondary lower alkyl (i.e., alkyl containing up to7 carbon atoms), phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, orhalohydrocarbonoxy wherein at least two carbon atoms separate thehalogen and oxygen atoms; and each Q² is independently hydrogen,halogen, primary or secondary lower alkyl, phenyl, haloalkyl,hydrocarbonoxy or halohydrocarbonoxy as defined for Q¹. In certainembodiments each Q¹ is alkyl or phenyl, especially C₁₋₄ alkyl, and eachQ² is hydrogen.

Both homopolymer and copolymer poly(phenylene ether)s are included. Inone embodiment homopolymers are those containing2,6-dimethyl-1,4-phenylene ether units. In one embodiment suitablecopolymers include random or block copolymers containing2,6-dimethyl-1,4-phenylene ether units in combination with (for example)2,3,6-trimethyl-1,4-phenylene ether units. Also included within thisclass of polymers are those produced by copolymerization of at least onemonophenol such as 2,6-dimethylphenol and a polyfunctional phenol suchas the bisphenol, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, so as toproduce a bifunctional phenol-containing polymer. Typical polyfunctionalphenols, and the resulting poly(phenylene ether) polymers produced fromthem, include those described in U.S. Pat. No. 5,352,745. Also includedare poly(phenylene ether)s containing moieties prepared by grafting ontothe poly(phenylene ether) in known manner such materials as vinylmonomers or polymers such as polystyrenes and elastomers, as well ascoupled poly(phenylene ether)s in which coupling agents such as lowmolecular weight polycarbonates, quinones, heterocycles and formalsundergo reaction in known manner with the hydroxy groups of twopoly(phenylene ether) chains to produce a higher molecular weightpolymer, provided that at least a portion of hydroxy groups remainsavailable for reaction with triazine moieties.

The poly(phenylene ether)s have an intrinsic viscosity (IV) in oneembodiment greater than about 0.08, in another embodiment greater thanabout 0.25, in another embodiment in the range of about 0.25-0.6 and instill another embodiment in the range of 0.4-0.6 dl./g., as measured inchloroform at 25° C. Mixtures of poly(phenylene ether)s with differentintrinsic viscosities are also suitable for use in the compositions ofthe invention. Such mixtures include those containing both low and highintrinsic viscosity poly(phenylene ether) resins such as is illustratedby 0.12 IV resin in combination with 0.46 IV resin.

The poly(phenylene ether)s are typically prepared by the oxidativecoupling of reactants comprising at least one monohydroxyaromaticcompound such as 2,6-xylenol or 2,3,6-trimethylphenol. Catalyst systemsare generally employed for such coupling; they typically contain atleast one heavy metal compound such as a copper, manganese or cobaltcompound, usually in combination with various other materials.Illustrative examples of catalysts and processes are disclosed in U.S.Pat. Nos. 3,306,874, 3,306,875, 3,914,266, 4,028,341, 4,054,553,4,092,294, 4,477,651, and 4,517,341.

In some embodiments poly(phenylene ether)s as synthesized contain atleast one aminoalkyl-containing end group. The aminoalkyl radical istypically located in an ortho position to the hydroxy group.Poly(phenylene ether)s containing such end groups may be obtained byincorporating an appropriate primary or secondary monoamine such asdi-n-butylamine or dimethylamine as one of the constituents of theoxidative coupling reaction mixture. Also frequently present are4-hydroxybiphenyl end groups, typically obtained from reaction mixturesin which a byproduct diphenoquinone is present, especially in acopper-halide-secondary or tertiary amine system. In one embodiment asubstantial proportion of the poly(phenylene ether) molecules, typicallyconstituting as much as about 90% by weight of the polymer, may containat least one of said aminoalkyl-containing and 4-hydroxybiphenyl endgroups.

In various embodiments low molecular weight PPE polymers may bedesirable to provide higher levels of phenol terminal-groups, enhanceflow, improve processability, or provide suitable homogeneity with otherblend components. Low molecular weight PPE polymers have in variousembodiments a number average molecular weight (Mn; as measured inchloroform at 25° C. versus polystyrene standards) of between about1,200 and about 9,700; in other embodiments the Mn is between about2,100 and about 5,900; and in still other embodiments the Mn is betweenabout 2,100 and about 3,900. As described above, these low molecularweight PPE polymers may be produced by oxidative polymerization.Alternatively, low molecular weight PPE polymers may be produced byother known methods such as by redistribution of PPE with a phenoliccompound in the presence of an oxidizing agent.

It will be apparent to those skilled in the art from the foregoing thatthe poly(phenylene ether)s contemplated for use in the present inventioninclude all those presently known which have nucleophilic groups,particularly nucleophilic end-groups, irrespective of variations instructural units or ancillary chemical features.

In another embodiment the present invention comprises polycarbonateswhich comprise triazine structural units. In various embodimentspolycarbonates of the present invention comprise structural unitsderived from at least one triazine-comprising compound, at least onedihydric phenol and a carbonate precursor. Suitable dihydric phenolsinclude those represented by the formula (XVII):HO-D-OH  (XVII)

wherein D is a divalent aromatic radical. In various embodiments D hasthe structure of formula (XVIII);

wherein A¹ represents an aromatic group such as phenylene, biphenylene,naphthylene, etc. E may be an alkylene or alkylidene group including,but not limited to, methylene, ethylene, ethylidene, propylene,propylidene, isopropylidene, butylene, butylidene, isobutylidene,amylene, amylidene, isoamylidene. When E is an alkylene or alkylidenegroup, it may also consist of two or more alkylene or alkylidene groupsconnected by a moiety different from alkylene or alkylidene, such as anaromatic linkage; a tertiary amino linkage; an ether linkage; a carbonyllinkage; a silicon-containing linkage; or a sulfur-containing linkageincluding, but not limited to, sulfide, sulfoxide, sulfone; or aphosphorus-containing linkage including, but not limited to, phosphinyl,phosphonyl. In addition, E may be a cycloaliphatic group including, butnot limited to, cyclopentylidene, cyclohexylidene,3,3,5-trimethylcyclohexylidene, methylcyclohexylidene,2-[2.2.1]-bicycloheptylidene, neopentylidene, cyclopentadecylidene,cyclododecylidene, adamantylidene; a sulfur-containing linkage, such assulfide, sulfoxide or sulfone; a phosphorus-containing linkage, such asphosphinyl or phosphonyl; an ether linkage; a carbonyl group; a tertiarynitrogen group; or a silicon-containing linkage such as silane orsiloxy. R⁷ represents hydrogen or a monovalent hydrocarbon group such asalkyl, aryl, aralkyl, alkaryl, or cycloalkyl. In various embodiments amonovalent hydrocarbon group of R⁷ may be halogen-substituted,particularly fluoro- or chloro-substituted, for example as indichloroalkylidene. Y² may be an inorganic atom including, but notlimited to, halogen (fluorine, bromine, chlorine, iodine); an inorganicgroup including, but not limited to, nitro; an organic group including,but not limited to, a monovalent hydrocarbon group such as alkyl, aryl,aralkyl, alkaryl, or cycloalkyl, or an oxy group such as OR⁸, wherein R⁸is a monovalent hydrocarbon group such as alkyl, aryl, aralkyl, alkaryl,or cycloalkyl; it being only necessary that Y² be inert to andunaffected by the reactants and reaction conditions used to prepare apolycarbonate. The letter “m” represents any integer from and includingzero through the number of positions on A¹ available for substitution;“p” represents an integer from and including zero through the number ofpositions on E available for substitution; “f” represents an integerequal to at least one; “s” is either zero or one; and “u” represents anyinteger including zero.

When more than one Y² substituent is present as represented by formula(XVIII) above, they may be the same or different. When more than one R⁷substituent is present, they may be the same or different. Where “s” iszero in formula (XVIII) and “u” is not zero, the aromatic rings aredirectly joined with no intervening alkylidene or other bridge. Thepositions of the hydroxyl groups and Y² on the aromatic residues A¹ canbe varied in the ortho, meta, or para positions and the groupings can bein vicinal, asymmetrical or symmetrical relationship, where two or morering carbon atoms of the aromatic residue are substituted with Y² andhydroxyl groups.

Some illustrative, non-limiting examples of dihydric phenols of formula(XVII) include the dihydroxy-substituted aromatic hydrocarbons disclosedby name or formula (generic or specific) in U.S. Pat. No. 4,217,438. Invarious embodiments of the invention dihydric phenols include6-hydroxy-1-(4′-hydroxyphenyl)-1,3,3-trimethylindane,4,4′-(3,3,5-trimethylcyclohexylidene)diphenol;1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane;2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol-A or“BPA”); 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane;2,2-bis(4-hydroxy-3-methylphenyl)propane;2,2-bis(4-hydroxy-3-ethylphenyl)propane;2,2-bis(4-hydroxy-3-isopropylphenyl)propane;2,4′-dihydroxydiphenylmethane; bis(2-hydroxyphenyl)methane;bis(4-hydroxy-phenyl)methane; bis(4-hydroxy-5-nitrophenyl)methane;bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane;1,1-bis(4-hydroxyphenyl)ethane; 1,1-bis(4-hydroxy-2-chlorophenyl)ethane;2,2-bis(3-phenyl-4-hydroxyphenyl)-propane;bis(4-hydroxyphenyl)cyclohexylmethane;2,2-bis(4-hydroxyphenyl)-1-phenylpropane; hydroquinone, resorcinol; C₁₋₃alkyl-substituted resorcinols.

Suitable dihydric phenols also include those containing indanestructural units such as represented by the formula (XIX), whichcompound is 3-(4-hydroxyphenyl)-1,1,3-trimethylindan-5-ol, and by theformula (XX), which compound is1-(4-hydroxyphenyl)-1,3,3-trimethylindan-5-ol:

Suitable dihydric phenols also include those containing spirobiindanestructural units such as represented by the formula (XXI):

wherein each R²⁰ is independently selected from monovalent hydrocarbonradicals and halogen radicals; each R²¹, R²², R²³, and R²⁴ isindependently C₁₋₆ alkyl; each R²⁵ and R²⁶ is independently H or C₁₋₆alkyl; and each n is independently selected from positive integershaving a value of from 0 to 3 inclusive. The monovalent hydrocarbonradicals represented by R²⁰ include alkyl radicals, cycloalkyl radicals,aryl radicals, aralkyl radicals, and alkaryl radicals, as alreadydefined hereinabove. In various embodiments the halogen radicalsrepresented by R²⁰ are fluorine, chlorine and bromine.

In the dihydric phenol compound of formula (XXI) when more than one R²⁰substituent is present they may be the same or different. The relativepositions of the hydroxyl groups and R²⁰ on the aromatic nuclearresidues may be varied in the ortho or meta positions. The position ofeach hydroxy group is independently at any unsubstituted site on each ofthe aromatic rings. In one embodiment each hydroxy group isindependently in positions 5 or 6 and 5′ or 6′ of each aromatic ring. Inanother embodiment each hydroxy group is in position 6 and 6′ of eacharomatic ring.

In various embodiments, each R²⁰ is independently selected fromchlorine, bromine, and lower alkyl radicals containing from 1 to about 5carbon atoms, each R²¹, R²², R²³, and R²⁴ is independently C₁₋₆ alkyl;each R²⁵ and R²⁶ is independently H or C₁₋₆ alkyl; and each n isindependently 0 to 3. In some embodiments, each R²⁰ is independentlyselected from chlorine and lower alkyl radicals containing from 1 toabout 3 carbon atoms, each R²¹, R²², R²³, and R²⁴ is independently C₁₋₂alkyl; each R²⁵ and R²⁶ is independently H or C₁₋₂ alkyl; and each n isindependently 0 to 2. In other embodiments, each R²¹, R²², R²³, and R²⁴is methyl; each R²⁵ and R²⁶ is H; and each n is 0.

In one embodiment a spiro dihydric phenol for forming polycarbonatessuitable for use in the present invention is6,6′-dihydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobiindane (sometimes knowas “SBI”), in which n in formula (XXI) is 0 and the linkages with therest of the polymer molecule are in a specific position on the aromaticrings.

In various embodiments the carbonate precursor for preparingpolycarbonates include at least one carbonyl halide, carbonate ester orhaloformate. The carbonyl halides which can be employed herein arecarbonyl chloride, carbonyl bromide and mixtures thereof. Typicalcarbonate esters which may be employed herein include, but are notlimited to, diaryl carbonates, including, but not limited to,diphenylcarbonate, di(halophenyl)carbonates, di(chlorophenyl)carbonate,di(bromophenyl)carbonate, di(trichlorophenyl)carbonate,di(tribromophenyl)carbonate; di(alkylphenyl)carbonates,di(tolyl)carbonate; di(naphthyl)carbonate, di(chloronaphthyl)carbonate,phenyl tolyl carbonate, chlorophenyl chloronaphthyl carbonate, di(methylsalicyl)carbonate, and mixtures thereof. The haloformates suitable foruse herein include bishaloformates of dihydric phenols, which include,but are not limited to, bischloroformates of hydroquinone; bisphenol-A;3-(4-hydroxyphenyl)-1,1,3-trimethylindan-5-ol;1-(4-hydroxyphenyl)-1,3,3-trimethylindan-5-ol;4,4′-(3,3,5-trimethylcyclohexylidene)diphenol;1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, and the like;bischloroformate-terminated polycarbonate oligomers such as oligomerscomprising hydroquinone, bisphenol-A,3-(4-hydroxyphenyl)-1,1,3-trimethylindan-5-ol;1-(4-hydroxyphenyl)-1,3,3-trimethylindan-5-ol;4,4′-(3,3,5-trimethylcyclohexylidene)diphenol,1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, or the like; andbishaloformates of glycols including, but not limited to,bishaloformates of ethylene glycol, neopentyl glycol, and polyethyleneglycol. Mixtures of haloformates may be employed. In a particularembodiment carbonyl chloride, also known as phosgene, is employed. Inanother particular embodiment diphenylcarbonate is employed.

Conditions for preparing polycarbonates include, but are not limited to,solution processes, interfacial processes, melt processes,transesterification processes, solid-state processes, and redistributionprocesses, and combinations thereof. Certain of these processes oftenemploy phosgene as carbonate precursor. Solution processes may comprisea stoichiometric amount of base such as triethylamine or pyridine. If aninterfacial process is used, the addition of various phase transfercatalysts is optional. Phase transfer catalysts which are suitableinclude, but are not limited, to tertiary amines, such as triethylamine,ammonium salts, such as tetrabutylammonium bromide; orhexaethylguanidinium chloride.

In one embodiment the polycarbonates are prepared by a melttransesterification process. This process does not require the use ofphosgene or a solvent, and often minimizes the formation of lowmolecular weight contaminants, such as cyclic and linear low molecularweight oligomers in the final polymer. In an illustrative examplepolycarbonate monomers are mixed with a carbonate source, such as adiarylcarbonate, and a small amount of catalyst, such as an alkali metalhydroxide or quaternary ammonium hydroxide or mixture thereof, andheated under a vacuum according to a protocol in which the temperatureis raised through a series of stages while the pressure in the headspaceover the reaction mixture is lowered from ambient pressure to about 1Torr. The time of the stages and the temperature are such thatmechanical losses of material through foaming and the like are avoided.In some embodiments the diarylcarbonate is diphenylcarbonate, and phenoland excess diphenylcarbonate may be removed overhead to complete thepolymerization process. At least one of optional end-capping agents,coupling agents, or branching agents which are well-known in the art orwhich are disclosed in the present invention may be included in thereaction if desired. The product high polymer may then be isolated as amelt which may be compounded with other additives, such as stabilizersand mold release agents prior to pelletization. Suitable carbonatesources, catalysts and reaction conditions may be found, for example, inU.S. Pat. No. 5,880,248, and Kirk-Othmer Encyclopedia of ChemicalTechnology, Fourth Edition, Volume 19, pp. 584-600, herein incorporatedby reference.

In various embodiments polycarbonates of the invention have a weightaverage molecular weight in a range of between about 5,000 and about100,000, in other embodiments a weight average molecular weight in arange of between about 10,000 and about 65,000, and in still otherembodiments a weight average molecular weight in a range of betweenabout 18,000 and about 55,000 as measured by gel permeationchromatography versus polystyrene standards. In other embodimentspolycarbonates of the invention have a weight average molecular weightin a range of between about 30,000 and about 55,000, as measured by gelpermeation chromatography versus polystyrene standards.

In one embodiment of the invention essentially all the polymer chains ofa triazine-comprising polymer have at least one nucleophilic groupattached thereto. In one embodiment essentially all the polymer chainshave at least one nucleophilic end-group. In another embodiment of theinvention only a portion of polymer chains have at least onenucleophilic group attached thereto. In another embodiment only aportion of polymer chains have at least one nucleophilic end-group. Inone embodiment of the invention essentially all the polymer nucleophilicgroups (for example, nucleophilic end-groups) are capped throughreaction with at least one triazine-comprising capping agent. In someembodiments essentially all the polymer chains have atriazine-comprising structural unit attached to at least two terminalsites on the polymer. In another embodiment of the invention only aportion of polymer nucleophilic groups (for example, nucleophilicend-groups) are capped through reaction with at least onetriazine-comprising capping agent. In other embodiments only a portionof the polymer chains have a triazine-comprising structural unitattached to at least two terminal sites on the polymer. In someembodiments a triazine-comprising capping agent may be employed incombination with at least one other non-triazine capping agent forreaction with monomer or polymer nucleophilic groups, particularlynucleophilic end-groups.

Depending upon what other functionality may be present on thetriazine-comprising capping agent and other factors such as reactionconditions and type of nucleophilic group on a polymer or monomer, thoseskilled in the art will realize that there may be circumstances in whicha triazine-comprising capping agent designed to be monofunctional (thatis, containing one L group) may react with a nucleophilic group to someminor extent at more than one site on the triazine ring, it being onlynecessary that the triazine substituent Z react with a nucleophilicgroup on a polymer or monomer at a slower rate than the leaving group L.Similarly a triazine-comprising capping agent designed to bedifunctional (that is, containing two L groups) may react with anucleophilic group to some minor extent at more than two sites on thetriazine ring, it being only necessary that the triazine substituent Zreact with a nucleophilic group on a polymer or monomer at a slower ratethan the leaving group L. It is often the case that substituents, suchas aryloxy, on a triazine ring become increasingly resistant toreaction, such as displacement or exchange, when they are stericallyhindered. In an illustrative example a 2,6-disubstituted aryloxy moietyis often more resistant to reaction with a nucleophilic group than itscorresponding mono-substituted aryloxy or unsubstituted aryloxy analog.

In various embodiments of the present invention polymers may comprise atriazine-comprising moiety as a terminal unit, or as a structural unitin the polymer chain other than at a terminal site, or both types ofstructural units. In the latter embodiment the mixture of types ofstructural units may be derived from reaction of nucleophile-containingpolymer or monomer with either one or more than one type oftriazine-comprising capping agent, for example a mixture of amonofunctional triazine-comprising capping agent and a difunctionaltriazine-comprising capping agent.

Difunctional triazine-comprising capping agents may be employed tochain-extend nucleophile-terminated polymers through reaction withterminal nucleophilic groups on more than one polymer chain. In suchembodiments the number average molecular weight of thetriazine-comprising polymer typically increases, and in one embodimentthe increase is at least 500 Daltons, in another embodiment at least1000 Daltons, in still another embodiment at least 2000 Daltons, and instill another embodiment at least 2500 Daltons. In other examples ofsuch embodiments the intrinsic viscosity of the triazine-comprisingpolymer typically increases, and in one embodiment the increase is atleast 0.05 IV units, in another embodiment at least 0.1 IV units, and instill another embodiment at least 0.2 IV units. IV units are usuallydeciliters per gram.

Trifunctional triazine-comprising capping agents may be employed tobranch nucleophile-terminated polymers through reaction with terminalnucleophilic groups on more than one polymer chain. In such embodimentsthe value for at least one viscosity value typically changes. Inparticular melt viscosity (as measured by DIN 54811) increases, or meltflow rate (as measured by ISO 1133) decreases, or melt volume rate (asmeasured by ISO 1133) decreases for the triazine-comprising polymer, andin one embodiment the change is at least 5%, in another embodiment atleast 10%, in still another embodiment at least 15%, in still anotherembodiment at least 20%, and in still another embodiment at least 50%compared to the polymer initial value.

Those skilled in the art will recognize that whether a difunctional ortrifunctional triazine-comprising capping agent reacts with nucleophilicgroups on more than one polymer chain may be at least partiallydependent upon the stoichiometric amount of capping agent added. Forexample, use of a stoichiometric excess of difunctionaltriazine-comprising capping agent may result in some portion of polymerchains being only end-capped with triazine moiety in addition topolymers chains being chain-extended. In one embodiment a substantialportion up to and including essentially all chains containing terminalnucleophilic groups may be simply end-capped if a large stoichiometricexcess of difunctional triazine-comprising capping agent in used. Inanother example, use of a stoichiometric excess of trifunctionaltriazine-comprising capping agent may result in a some portion ofpolymer chains being only chain-extended or end-capped with triazinemoiety in addition to polymers chains being branched. In one embodimentthe present invention encompasses both the product thereof and theprocess of using a difunctional triazine-comprising capping agent toprovide a polymer comprising a mixture of end-capped and chain-extendedchains. In other embodiments the present invention also encompasses boththe product thereof and the process of using a trifunctionaltriazine-comprising capping agent to provide a polymer comprising amixture of chain-extended and branched chains or a mixture ofend-capped, chain-extended, and branched chains.

In another embodiment polymers with nucleophilic groups capped throughreaction with a triazine-comprising capping agent may be used aspolymerization promoters for growing a polymer chain from at least onepoint of the capped polymer. In one embodiment polymers withnucleophilic groups end-capped through reaction with a di- ortrifunctional triazine or chain-extended with a trifunctional triazinemay be used as polymerization promoters for growing a polymer chain fromat least one point of the capped polymer. In a particular embodiment apolycarbonate comprising at least one triazine structural unit whereinthe triazine structural unit possesses at least one L group may be usedin reaction with at least one dihydric phenol and carbonate precursor togrow a new polycarbonate chain attached to the initial polycarbonatechain through a triazine moiety.

Polymers or monomers comprising nucleophilic groups may be combined andreacted with triazine-comprising capping agents using any known method.Representative methods include, but are not limited to, solutionmethods, interfacial methods, melt methods, slurry methods, solid-statemethods, and combinations thereof. Any method employed may be a batchmethod, semi-continuous method, or continuous method. The amount oftriazine-comprising capping agent employed will generally depend uponthe level of nucleophilic groups contained in a polymer or monomer, andthe desired level of triazine-comprising compound to be incorporatedinto a final product. In one embodiment the amount oftriazine-comprising capping agent employed is in a range of betweenabout 5 mole % and about 400 mole %; in another embodiment in a range ofbetween about 20 mole % and about 200 mole %; in another embodiment in arange of between about 40 mole % and about 150 mole %; in still anotherembodiment in a range of between about 60 mole % and about 120 mole %based on moles nucleophilic groups contained in the polymer or monomer.

In one embodiment of the present invention polymers or monomerscomprising nucleophilic groups are reacted with triazine-comprisingcapping agents in the presence of at least one catalyst. Suitablecatalysts comprise those known to effect transesterification reactions.In various embodiments such catalysts comprise acidic, neutral, or basiccatalysts, such classifications often being based on the reaction of aconventional acid-base indicator and the catalyst when the latter isdissolved in a polar ionizing solvent such as water. In one embodiment abasic catalyst is employed. Suitable basic catalysts comprise the alkalimetals, examples of which comprise lithium, sodium, potassium, rubidium,and cesium; and their corresponding carbonates, hydroxides, hydrides,borohydrides, phenates, bisphenates, (that is, salt of a bisphenol);carboxylates such as acetate or benzoate; fluorides; and oxides. GroupII and III elements can also be used in place of the alkali metals ofthe foregoing classes of compounds such as metals and compounds ofcalcium, magnesium and aluminum. Other bases comprise trialkyl ortriaryl tin hydroxides, acetates, phenates, and the like. In particularembodiments examples of catalysts comprise lithium, sodium, potassium,rubidium, and cesium metals; lithium hydride, aluminum tri-isopropoxideand triphenyl tin hydroxide.

In other embodiments catalysts comprise metal oxides, metal acetates,titanium, and tin compounds. Suitable metal oxides comprise antimonytrioxide, germanium oxide, arsenic trioxide, lead oxide, magnesiumoxide, and zinc oxide. Suitable metal acetates comprise cobalt acetate,zinc acetate, cadmium acetate and manganese acetate. Suitable titaniumcompounds comprise the titanates such as tetrabutyl titanate andtetraisopropyl titanate. Suitable tin compounds comprise dibutyl tinoxide, dibutyl tin methoxide and dibutyl tin dilaurate.

In other particular embodiments illustrative examples of catalystscomprise at least one nitrogen-containing basic compound,phosphorus-containing basic compound, alkali metal compound, alkalineearth metal compound, or a boric acid or boric ester. Mixtures of suchcatalysts may also be employed.

In various embodiments nitrogen-containing basic compounds comprisealkyl-, aryl-, or alkaryl quaternary ammonium hydroxides such astetramethylammonium hydroxide, tetraethylammonium hydroxide,tetrabutylammonium hydroxide and trimethylbenzylammonium hydroxide;tertiary amines represented by R₃N (wherein R is alkyl or aryl or amixture thereof) such as trimethylamine, triethylamine,dimethylbenzylamine and triphenylamine; secondary amines represented byR₂NH (wherein R is as defined above); primary amines represented by RNH₂(wherein R is as defined above); ammonia; or basic salts such astetramethylammonium borohydride, tetrabutylammonium borohydride,tetrabutylammonium tetraphenyl borate, tetramethylammonium tetraphenylborate, and hexaalkylguanidinium salts andalpha,omega-bis(pentaalkylguanidinium)alkane salts, comprisinghexaethylguanidinium halides,alpha,omega-bis(pentaalkylguanidinium)alkane halides, andhexaethylguanidinium chloride. In various embodimentsphosphorus-containing basic compounds comprise quaternary phosphoniumhydroxides and quaternary phosphonium carboxylates, such astetrabutylphosphonium acetate.

In various embodiments alkali metal compounds comprise sodium hydroxide,potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate,potassium hydrogencarbonate, lithium hydrogencarbonate, sodiumcarbonate, potassium carbonate, lithium carbonate, sodium acetate,potassium acetate, lithium acetate, sodium stearate, potassium stearate,lithium stearate, sodium borohydride, potassium borohydride, lithiumborohydride, sodium borophenylate, sodium benzoate, potassium benzoate,lithium benzoate, disodium hydrogenphosphate, dipotassiumhydrogenphosphate, dilithium hydrogenphosphate, disodium salt ofbisphenol A, dipotassium salt of bisphenol A, dilithium salt ofbisphenol A, sodium phenylate, potassium phenylate, and lithiumphenylate.

In various embodiments alkaline earth metal compounds comprise calciumhydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide,calcium hydrogencarbonate, barium hydrogencarbonate, magnesiumhydrogencarbonate, strontium hydrogencarbonate, calcium carbonate,barium carbonate, magnesium carbonate, strontium carbonate, calciumacetate, barium acetate, magnesium acetate, strontium acetate, calciumstearate, barium stearate, magnesium stearate and strontium stearate.

In various embodiments boric acid or boric acid ester compounds compriseboric acid and boric acid esters represented by the general formulaB(OR)_(n)(OH)_(3-n) (wherein R is alkyl or aryl, and n is 1, 2 or 3),and boric acid esters comprising trimethyl borate, triethyl borate,tributyl borate, trihexyl borate, triheptyl borate, triphenyl borate,tritolyl borate and trinaphthyl borate.

Catalyst may be present in one embodiment at a total level of about 10⁻⁸moles to about 0.1 moles, in another embodiment at a total level ofabout 10⁻⁸ moles to about 0.06 moles, in another embodiment at a totallevel of about 10⁻⁸ moles to about 0.02 moles, in another embodiment ata total level of about 10⁻⁷ moles to about 0.02 moles, in anotherembodiment at a total level of about 10⁻⁶ moles to about 0.02 moles, inanother embodiment at a total level of about 10⁻⁵ moles to about 0.02moles, in another embodiment at a total level of about 10⁻⁴ moles toabout 0.02 moles, and in still another embodiment at a total level ofabout 10⁻³ moles to about 0.02 moles, in all cases per mole of polymerrepeat unit, or in the case of polycarbonates per mole of the aromaticdihydroxy compound.

In various embodiments the amount of the nitrogen containing basiccompound employed is in one embodiment from about 10⁻⁶ moles to about10⁻¹ moles and in another embodiment from about 10⁻⁵ moles to about 10⁻²moles, in all cases per mole of polymer repeat unit, or in the case ofpolycarbonates per mole of the aromatic dihydroxy compound. The amountof the alkali metal or alkaline earth metal compound employed is in oneembodiment from about 10⁻⁸ moles to about 10⁻³ moles, in anotherembodiment from about 10⁻⁷ moles to about 10⁻⁴ moles, and in stillanother embodiment from about 10⁻⁷ moles to about 10⁻⁵ moles, in allcases per mole of polymer repeat unit, or in the case of polycarbonatesper mole of the aromatic dihydroxy compound. The amount of the boricacid or boric acid ester is in one embodiment from about 10⁻⁸ moles toabout 10⁻¹ moles, in another embodiment from about 10⁻⁷ moles to about10⁻² moles, and in still another embodiment from about 10⁻⁶ moles toabout 10⁻⁴ moles, in all cases per mole of polymer repeat unit, or inthe case of polycarbonates per mole of the aromatic dihydroxy compound.

Prior to its combination with one or more reactants or its introductioninto a reaction mixture, a catalyst may be in liquid form, for examplein the case of solid catalysts through melting or through dissolution ina liquid or normally solid, low melting solvent. In various embodimentssolvents comprise phenol and substituted phenols. Substituted phenolswhich can be used comprise those comprising at least one substituent R,wherein R comprises alkyl of 1 to 10 carbon atoms, alkoxy of 1 to 10carbon atoms, aryl of 6 to 10 carbon atoms, chloro, bromo or mixturesthereof. Illustrative examples of solvents comprise o-benzyl-phenol,o-bromophenol, m-bromophenol, m-chlorophenol, p-chlorophenol,2,4-dibromophenol, 2,6-dichlorophenol, 3,5-dimethoxyphenol,o-ethoxyphenol, m-ethyl-phenol, p-ethylphenol, o-isopropylphenol,m-methoxyphenol, m-propylphenol, p-propylphenol, and the like. In otherembodiments solvents may be of the ether type, for example,tetrahydrofuran and the various glymes, for example, ethylene glycoldimethylether and the like. Liquid phosphites such as triphenylphosphite and tris(nonylphenyl)phosphite, and phosphates such astrimethyl or triethyl phosphate are also useful in diluents. In oneembodiment any solvent or diluent used with a catalyst corresponds to aleaving group compound derived from triazine-comprising capping agent.Combinations of catalysts and combinations of solvents may also be used.In various embodiments when a basic catalyst is employed, the catalystmay be introduced concurrently with the aforementioned molten reactantsto the polymerization to avoid heating the reactants in the presence ofthe catalyst prior to onset of the transesterification.

In one embodiment combination and reaction of polymer or monomer withtriazine-comprising capping agent is performed in any type ofmelt-processing equipment, illustrative examples of which include a meltmixer and an extruder. In another embodiment, when a polymer is liquidor low viscosity at room temperature, combination of polymer or monomerwith triazine-comprising capping agent may be performed in any type ofmixing equipment, optionally in the presence of a solvent for eitherpolymer or monomer, or triazine compound or both, and typically withheating. In various embodiments the order of mixing oftriazine-comprising capping agent with polymer or monomer may compriseadding triazine compound to any reaction equipment before adding thepolymer or monomer to be reacted, or combining triazine compound withpolymer or monomer and then adding to any reaction equipment, or addingtriazine compound to any reaction equipment after the polymer ormonomer, for example through addition of triazine compound at adown-stream feedport of an extruder to which polymer or monomer has beenfed at an initial feedport. In various embodiments addition of triazinecompound to an extruder may be by liquid or melt injection or using aside-feeder. Also in various embodiments triazine-comprising cappingagent may be combined with polymer or monomer as the triazine compounditself, or as a solution or slurry of triazine compound in a solvent, oras a mixture with another substance, for example as a concentrate oftriazine compound in a polymer or monomer, for example the polymer forwhich the triazine compound is to serve as a nucleophile-capper. Anymethod used for reacting polymers or monomers with triazine-comprisingcapping agents may beneficially comprise a process step fordevolatilization of leaving group compound. For example a melt mixer oran extruder or a horizontally agitated polymerization tank used forreacting polymers or monomers with triazine-comprising capping agentsmay comprise a devolatilization step. In the case of an extruder adevolatilization step may comprise applying reduced pressure at one ormore extruder barrel segment downstream of any extruder reaction zone.If desired, leaving group compound may be recovered and recycled usingknown methods. In one embodiment leaving group compound is recycled foruse in reaction to make triazine-comprising capping agent. In oneembodiment in an extrusion process subsequent feedports or furthermolding and extrusion processes may be used to add commonly knownadditives such as, for example, antioxidants, antistatic agents, inertfillers, ultraviolet radiation absorbers and stabilizers, hydrolyticstabilizers, impact modifiers, mold release agents, color stabilizers,flame retardants, and the like. Whatever process is used, anucleophile-capped polymer is isolated using standard methods including,if desired, converting the polymer into pellets. In one embodimentpolymers comprising nucleophilic groups are reacted withtriazine-comprising capping agents in a melt process in which aprocessing aid has been adding to the mixture. Examples of processingaids include known plasticizers and also miscible polymers, such aspolystyrene which is miscible with poly(phenylene ether)s.

In a particular embodiment a triazine-comprising capping agent may becombined with a polycarbonate or polycarbonate monomers at some stage ofa melt polycarbonate synthesis. In a particular embodiment atriazine-comprising capping agent may be employed in a manner such as toallow polycarbonate polymerization to be carried out rapidly at close tostoichiometric conditions until a desired molecular weight is achievedand then to allow rapid increase in the endcap level and/or molecularweight of the polycarbonate to a desired level by adding the endcappingagent. Polycarbonates end-capped with triazine-comprising moieties oftenhave beneficial properties such as at least one of improved impactstrength, improved melt flow rate, improved optical properties, andimproved adhesion to metal.

In various embodiments the triazine-comprising polymers of the presentinvention may further comprise additives known in the art, which may beadded by any known method. Illustrative additives include, but are notlimited to, pigments, dyes, impact modifiers, UV screeners, radiationscreeners, flame retardants, fillers, heat stabilizers, colorstabilizers, flow aids, ester interchange inhibitors, antistatic agents,hydrolytic stability improvers, chemical resistance improvers,dimensional stability improvers, weatherability improvers, glossimprovers, water repellents, anti-staining aids, metal flakes, adhesionpromoters, and mold release agents.

Articles comprising a polymer comprising triazine structural units areanother embodiment of the present invention. In various embodimentsarticles may consist essentially of polymers comprising triazinestructural units or, if desired, said polymers in admixture with polymeradditives known in the art.

In one embodiment articles are prepared from polycarbonates comprisingtriazine structural units. Such articles may possess advantageousproperties such as low water absorption, good processability and lowbirefringence, and they can be advantageously utilized to produceoptical articles. End-use applications for optical articles include, butare not limited to, a digital audio disk, a digital versatile disk, anoptical memory disk, a compact disk, an ASMO device and the like;optical lenses, such as contact lenses, lenses for glasses, lenses fortelescopes, and prisms; optical fibers; magneto optical disks;information recording media; information transferring media; disks forvideo cameras, disks for still cameras and the like.

In other embodiments articles of the present invention are multilayerarticles comprising two or more layers, typically in contiguoussuperposed contact with one another. In various embodiments multilayerarticles comprise a substrate layer comprising at least onethermoplastic polymer, thermoset polymer, cellulosic material, glass,ceramic, or metal, and at least one coating layer thereon, said coatinglayer comprising a triazine-comprising polymer, particularly apolycarbonate comprising triazine structural units. Optionally, themultilayer articles may further comprise an interlayer, for example anadhesive interlayer (or tie layer), between any substrate layer and anycoating layer comprising a triazine-comprising polymer. Multilayerarticles of the invention include, but are not limited to, those whichcomprise a substrate layer and a coating layer comprising atriazine-comprising polymer; those which comprise a substrate layer witha coating layer comprising said polymer on each side of said substratelayer; and those which comprise a substrate layer and at least onecoating layer comprising a triazine-comprising polymer with at least oneinterlayer between a substrate layer and a coating layer. Any interlayermay be transparent and/or may contain an additive, for example acolorant or decorative material such as metal flake. If desired, anoverlayer may be included over the coating layer comprising atriazine-comprising polymer, for example to provide abrasion or scratchresistance. In one embodiment the substrate layer, coating layercomprising a triazine-comprising polymer, and any interlayers orovercoating layers are in contiguous superposed contact with oneanother. In any embodiment a triazine-comprising polymer layer maycomprise conventional additives known in the art for use with polymers,including conventional UV screeners, heat stabilizers, flow promoters,lubricants, dyes, pigments, and the like. In one embodiment a triazinecomprising polymer is a polycarbonate, for example a bisphenol Apolycarbonate.

Representative articles which can be made which comprise compositions ofthe invention include aircraft, automotive, truck, military vehicle(including automotive, aircraft, and water-borne vehicles), andmotorcycle exterior and interior components, including panels, quarterpanels, rocker panels, trim, fenders, doors, decklids, trunklids, hoods,bonnets, roofs, bumpers, fascia, grilles, mirror housings, pillarappliques, cladding, body side moldings, wheel covers, hubcaps, doorhandles, spoilers, window frames, headlamp bezels, headlamps, taillamps, tail lamp housings, tail lamp bezels, license plate enclosures,roof racks, and running boards; enclosures, housings, panels, and partsfor outdoor vehicles and devices; enclosures for electrical andtelecommunication devices; outdoor furniture; boats and marineequipment, including trim, enclosures, and housings; outboard motorhousings; depth finder housings, personal water-craft; jet-skis; pools;spas; hot-tubs; steps; step coverings; building and constructionapplications such as glazing, roofs, windows, floors, decorative windowfurnishings or treatments; treated glass covers for pictures, paintings,posters, and like display items; optical lenses; ophthalmic lenses;corrective ophthalmic lenses; implantable ophthalmic lenses; wallpanels, and doors; protected graphics; outdoor and indoor signs;enclosures, housings, panels, and parts for automatic teller machines(ATM); enclosures, housings, panels, and parts for lawn and gardentractors, lawn mowers, and tools, including lawn and garden tools;window and door trim; sports equipment and toys; enclosures, housings,panels, and parts for snowmobiles; recreational vehicle panels andcomponents; playground equipment; articles made from plastic-woodcombinations; golf course markers; utility pit covers; computerhousings; desk-top computer housings; portable computer housings;lap-top computer housings; palm-held computer housings; monitorhousings; printer housings; keyboards; FAX machine housings; copierhousings; telephone housings; mobile phone housings; radio senderhousings; radio receiver housings; light fixtures; lighting appliances;network interface device housings; transformer housings; air conditionerhousings; cladding or seating for public transportation; cladding orseating for trains, subways, or buses; meter housings; antenna housings;cladding for satellite dishes; coated helmets and personal protectiveequipment; coated synthetic or natural textiles; coated photographicfilm and photographic prints; coated painted articles; coated dyedarticles; coated fluorescent articles; coated foam articles; and likeapplications. The invention further contemplates additional fabricationoperations on said articles, such as, but not limited to, molding,in-mold decoration, baking in a paint oven, lamination, and/orthermoforming.

Without further elaboration, it is believed that one skilled in the artcan, using the description herein, utilize the present invention to itsfullest extent. The following examples are included to provideadditional guidance to those skilled in the art in practicing theclaimed invention. While some of the examples are illustrative ofvarious embodiments of the claimed invention, others are comparative.The examples provided are merely representative of the work thatcontributes to the teaching of the present application. Accordingly,these examples are not intended to limit the invention, as defined inthe appended claims, in any manner.

The following examples illustrate syntheses of triazine-comprisingcompounds.

EXAMPLE 1 Synthesis of2-chloro-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine

A solution of 27.7 grams (g) (0.15 moles) cyanuric chloride, 36.6 g(0.30 moles) 2,6-xylenol and 0.97 g (0.003 moles) tetra-n-butylammoniumchloride in 250 milliliters (ml) of to toluene was chilled in anice-water bath. To the stirred solution was slowly added a solution ofsodium hydroxide, 12.0 g (0.3 moles) in 25 ml of water. The mixture wasmaintained at a temperature below about 20° C. for two hours and thenstirred at room temperature for an additional 16 hours. The resultingmixture was filtered. The collected solids were washed with water. Thecombined filtrate and washes were transferred to a separatory funnel andthe aqueous phase was discarded. The organic phase was washedsequentially with equal portions of 10% aqueous hydrochloric acid, waterand saturated sodium chloride solution. Evaporation of the organic phaseafforded an off-white solid which was combined with the solids from thefiltration of the reaction mixture. Recrystallization of these solidsfrom a mixture of toluene and hexane afforded pure2-chloro-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine, melting point161-162° C.

EXAMPLE 2 Synthesis of2-(2-carbomethoxyphenoxy)-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine

A 250 ml 3-neck flask equipped with a condenser, a nitrogen inlet, amagnetic stirrer and an addition funnel was charged with sodium hydride(3.0 g of a 60% dispersion in oil; 0.075 moles). The dispersion wasrinsed twice with hexane followed by decantation. The flask was thencharged with 60 ml of dry N-methyl-2-pyrrolidinone (NMP) and methylsalicylate, 11.4 g (0.075 moles). The resulting mixture was stirreduntil no further hydrogen evolution was noted. To this mixture was addeddropwise, a solution of2-chloro-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine (25 g; 0.07 moles)in a minimal amount of dry NMP. This mixture was heated at 60° C. forthree hours at which point liquid chromatographic analysis indicatedthat no more of the triazine starting material was present. The solutionwas poured into 200 ml of ice-water containing a little hydrochloricacid. The resulting slurry was extracted three times with 150 mlportions of dichloromethane. Combined extracts were washed sequentiallywith equal portions of 10% aqueous hydrochloric acid, 5% aqueous sodiumhydroxide, water and brine. Evaporation of the organic phase afforded anoil which solidified to a foam by drying in a cooling bath under to highvacuum. The foam fused to a glass at 50° C. and the glass liquefied atbetween 85-90° C. The proton (¹H) nuclear magnetic resonance (NMR)spectrum was consistent with the desired product,2-(2-carbomethoxyphenoxy)-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine.

EXAMPLE 3 Synthesis of2-chloro-4,6-bis(2,4,6-tribromophenoxy)-1,3,5-triazine

The procedure of Example 1 is essentially repeated except that twoequivalents of 2,4,6-tribromophenol is used in place of 2,6-xylenol. Theproduct is the desired2-chloro-4,6-bis(2,4,6-tribromophenoxy)-1,3,5-triazine.

EXAMPLE 4 Synthesis of2-(2-carbomethoxyphenoxy)-4,6-bis(2,4,6-tribromophenoxy)-1,3,5-triazine

The procedure of Example 2 is essentially repeated except that2-chloro-4,6-bis(2,4,6-tribromophenoxy)-1,3,5-triazine is used in placeof 2-chloro-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine. The product isthe desired2-(2-carbomethoxyphenoxy)-4,6-bis(2,4,6-tribromophenoxy)-1,3,5-triazine.

EXAMPLE 5 Synthesis of2,4-bis(2-carbomethoxyphenoxy)-6-(2,4,6-trimethylphenoxy)-1,3,5-triazine

The procedure of Example 2 is essentially repeated except that oneequivalent of 2,4-dichloro-6-(2,4,6-trimethylphenoxy)-1,3,5-triazine(synthesized as described in U.S. Pat. No. 5,229,513) is used along withabout 2 equivalents of methyl salicylate. The product is the desired2,4-bis(2-carbomethoxyphenoxy)-6-(2,4,6-trimethylphenoxy)-1,3,5-triazine.

EXAMPLE 6 Synthesis of 2-allyloxy-4,6-dichloro-1,3,5-triazine

A solution of 91.8 grams (g) (0.49 moles) cyanuric chloride in 400 ml ofdichloromethane was treated with 28.91 g (0.49 moles) allyl alcohol, andthe mixture was chilled in an ice-water bath to about 0-5° C. Theice-water bath was removed and 45.79 g 50% aqueous sodium hydroxide wasadded over about 30 minutes with stirring keeping the temperaturebetween about 0° C. and about 10° C. Stirring was continued for anadditional 30 minutes after which time the layers were separated and theorganic layer washed two times with water, and the solution was driedover magnesium sulfate. Filtration and evaporation of the solutionafforded a mobile liquid. The proton and carbon nuclear magneticresonance (NMR) spectra were consistent with the desired product,2-allyloxy-4,6-dichloro-1,3,5-triazine.

EXAMPLE 7 Synthesis of2-allyloxy-4,6-bis(2-carbomethoxyphenoxy)-1,3,5-triazine

The procedure of Example 2 is essentially repeated except that oneequivalent of 2-allyloxy-4,6-dichloro-1,3,5-triazine is used along withabout 2 equivalents of methyl salicylate. The product is the desired2-allyloxy-4,6-bis(2-carbomethoxyphenoxy)-1,3,5-triazine.

EXAMPLE 8 Synthesis of 2,4-dichloro-6-glycidoxy-1,3,5-triazine

A solution of 73.76 g (0.4 moles) cyanuric chloride in 360 ml ofdichloromethane was chilled in an ice-water bath to about 0-5° C. and31.85 g (0.43 moles) glycidol was added. A solution of 34.4 g 50%aqueous sodium hydroxide was added over about 30-45 minutes withstirring keeping the temperature between about 0° C. and about 10° C.Stirring was continued for an additional 3 hours after which time thelayers were separated and the organic layer washed two times with water,and once with brine and the solution was dried over magnesium sulfate.Filtration and evaporation of the solution afforded a white solid, asample of which was further purified by trituration with hexane-ethylacetate. The proton and carbon nuclear magnetic resonance (NMR) spectrawere consistent with the desired product,2,4-dichloro-6-glycidoxy-1,3,5-triazine.

EXAMPLE 9 Synthesis of2,4-bis(2-carbomethoxyphenoxy)-6-glycidoxy-1,3,5-triazine

The procedure of Example 2 is essentially repeated except that oneequivalent of 2,4-dichloro-6-glycidoxy-1,3,5-triazine is used along withabout 2 equivalents of methyl salicylate. The product is the desired2,4-bis(2-carbomethoxyphenoxy)-6-glycidoxy-1,3,5-triazine.

EXAMPLE 10 Synthesis of2,4-dichloro-6-(2-methoxy-2-methyl-1,3-dioxolanyl)methoxy-1,3,5-triazine

The procedure of Example 8 is essentially repeated except that oneequivalent of 4-hydroxymethyl-2-methoxy-2-methyl-1,3-dioxolane is usedin place of glycidol, and triethylamine and a phase transfer catalystare both added to the reaction mixture before treatment with aqueoussodium hydroxide. The product is the desired2,4-dichloro-6-(2-methoxy-2-methyl-1,3-dioxolanyl)methoxy-1,3,5-triazine.

EXAMPLE 11 Synthesis of2,4-bis(2-carbomethoxyphenoxy)-6-(2-methoxy-2-methyl-1,3-dioxolanyl)methoxy-1,3,5-triazine

The procedure of Example 2 is essentially repeated except that oneequivalent of2,4-dichloro-6-(2-methoxy-2-methyl-1,3-dioxolanyl)methoxy-1,3,5-triazineis used along with about 2 equivalents of methyl salicylate. The productis the desired2,4-bis(2-carbomethoxyphenoxy)-6-(2-methoxy-2-methyl-1,3-dioxolanyl)methoxy-1,3,5-triazine.

EXAMPLE 12 Synthesis of2-(2-carbomethoxyphenoxy)-4-(2-methoxy-2-methyl-1,3-dioxolanyl)methoxy-6-(2,4,6-trimethylphenoxy)-1,3,5-triazine

The procedure of Example 2 is essentially repeated except that oneequivalent of2-chloro-4-(2-methoxy-2-methyl-1,3-dioxolanyl)methoxy-6-(2,4,6-trimethylphenoxy)-1,3,5-triazineis used along with about 1 equivalent of methyl salicylate. The productis the desired2-(2-carbomethoxyphenoxy)-4-(2-methoxy-2-methyl-1,3-dioxolanyl)methoxy-6-(2,4,6-trimethylphenoxy)-1,3,5-triazine.

EXAMPLE 13 Synthesis of2-butoxy-4-(2-carbomethoxyphenoxy)-6-glycidoxy-1,3,5-triazine

The procedure of Example 2 is essentially repeated except that oneequivalent of2-butoxy-4-chloro-6-(2,4,6-trimethylphenoxy)-1,3,5-triazine (synthesizedas described in U.S. Pat. No. 4,895,945) is used along with about 1equivalent of methyl salicylate. The product is the desired2-butoxy-4-(2-carbomethoxyphenoxy)-6-glycidoxy-1,3,5-triazine.

EXAMPLE 14 Synthesis of2-(2-carbomethoxyphenoxy)-4,6-diglycidoxy-1,3,5-triazine

The procedure of Example 2 is essentially repeated except that oneequivalent of 2-chloro-4,6-diglycidoxy-1,3,5-triazine (synthesized asdescribed in U.S. Pat. No. 4,895,945) is used along with about 1equivalent of methyl salicylate. The product is the desired2-(2-carbomethoxyphenoxy)-4,6-diglycidoxy-1,3,5-triazine.

EXAMPLE 15 Synthesis of2-(2-carbomethoxyphenoxy)-4-glycidoxy-6-(2,4,6-trimethylphenoxy)-1,3,5-triazine

The procedure of Example 2 is essentially repeated except that oneequivalent of2-chloro-4-glycidoxy-6-(2,4,6-trimethylphenoxy)-1,3,5-triazine is usedalong with about 1 equivalent of methyl salicylate. The product is thedesired2-(2-carbomethoxyphenoxy)-4-glycidoxy-6-(2,4,6-trimethylphenoxy)-1,3,5-triazine.

EXAMPLE 16 Synthesis of2-chloro-4-(4-ethenylphenoxy)-6-(2,4,6-trimethylphenoxy)-1,3,5-triazine

A solution of 25.57 g (0.09 moles)2,4-dichloro-6-(2,4,6-trimethylphenoxy)-1,3,5-triazine in 300 ml ofdichloromethane was treated with 11.8 g (0.098 moles) p-hydroxystyrene(prepared by hydrolysis of p-acetoxystyrene) dissolved in about 40 mldichloromethane. The mixture was cooled in an ice-water bath and 36.8 gof 10% aqueous sodium hydroxide solution was added with stirring overabout 5 minutes. Stirring was continued for 30 minutes after which timethe ice-water bath was removed and stirring was continued for about 2hours. The mixture was treated with brine, the layers were separated,and after standing, the organic layer was washed twice with brine, andonce with water, and dried over magnesium sulfate. Filtration andevaporation gave a white solid with proton NMR spectrum consistent withthe desired product,2-chloro-4-(4-ethenylphenoxy)-6-(2,4,6-trimethylphenoxy)-1,3,5-triazine.

EXAMPLE 17 Synthesis of2-(2-carbomethoxyphenoxy)-4-(4-ethenylphenoxy)-6-(2,4,6-trimethylphenoxy)-1,3,5-triazine

The procedure of Example 2 is essentially repeated except that oneequivalent of2-chloro-4-(4-ethenylphenoxy)-6-(2,4,6-trimethylphenoxy)-1,3,5-triazineis used along with about 1 equivalent of methyl salicylate. The productis the desired2-(2-carbomethoxyphenoxy)-4-(4-ethenylphenoxy)-6-(2,4,6-trimethylphenoxy)-1,3,5-triazine.

EXAMPLE 18 Synthesis of 2,4,6-tris(2-carbomethoxyphenoxy)-1,3,5-triazine

A solution of 13.8 grams (g) (0.075 moles) cyanuric chloride in 400 mlof dichloromethane was treated with 35.7 g (0.2346 moles) methylsalicylate and 0.7 g Adogen 464, and the mixture was chilled in anice-water bath to about 6° C. The ice-water bath was removed and 18.8 g50% aqueous sodium hydroxide was added over 10 minutes with stirring.Stirring was continued for about 16 hours after which time the layerswere separated and the organic layer washed four times with 2% aqueoussodium hydroxide, twice with water, once with brine, and the solutionwas dried over magnesium sulfate. Filtration and evaporation of thesolution afforded an off-white solid with melting point about 58-63° C.The proton and carbon nuclear magnetic resonance (NMR) spectra wereconsistent with the desired product,2,4,6-tris(2-carbomethoxyphenoxy)-1,3,5-triazine.

The following examples illustrate syntheses of polymers comprisingtriazine-comprising structural units. The properties of polycarbonateswere measured as follows. Weight average molecular weights (Mw) andnumber average molecular weights (Mn) were measured by gel permeationchromatography (GPC) versus polystyrene standards using polymersolutions at a concentration of 1 milligram per ml in dichloromethane.Free hydroxy end-group concentration (sometimes referred to as free-OHcontent) was measured by UV/Visible analysis of the complexes formedfrom the polymer with titanium tetrachloride in dichloromethanesolution. Polycarbonate endcap levels in percent were calculated fromthe free OH content and Mn values using the equation${\%\quad E\quad C} = {100 - \frac{{M_{n}\left( {P\quad C} \right)} \cdot W_{{free}\quad O\quad H}}{{2 \cdot 17 \cdot 10}{,000}}}$

wherein W_(free OH) is the concentration of free OH groups in ppm.

EXAMPLE 19

A BPA polycarbonate prepared by a melt process was endcapped using anactivated triazine. The BPA polycarbonate initially had Mw 18,300, Mn7,520, free-OH content of 670 parts per million (ppm), and an endcaplevel of 84.6%. A batch reactor tube was charged with 25 g of BPApolycarbonate and 0.511 g (1.084×10⁻³ moles)2-(2-carbomethoxyphenoxy)-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazineunder nitrogen. The mixture was heated to a temperature of 300° C. andstirred for 20 minutes. After the melt mixing stage, vacuum was appliedto the system to a pressure of about 50 pascals. Under these conditionsthe reaction was continued for 20 minutes. After the reaction stage, thepolymer was removed from the reaction tube and purified byreprecipitation. The endcap level of the polycarbonate increased from84.6% to 92.4% and the free-OH content decreased from 670 to 290 ppm.The amount of triazine endcap incorporated into the capped polymer wascalculated to be 0.64 mole % (or 1.1 mass %) based on moles BPA anddetermined by integration of the 2.05 ppm (s, 12H, ArCH₃) peak in the ¹HNMR (CDCl₃) spectrum of the purified polymer product. The results areshown in Table 1.

EXAMPLE 20

A batch reactor tube was charged with 25 g of BPA polycarbonate and1.250 g (2.651×10⁻³ moles)2-(2-carbomethoxyphenoxy)-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazineunder nitrogen. To the reactor tube 100 microliters of an aqueous sodiumhydroxide catalyst solution (4.67×10⁻³ molar concentration) was added.The mixture was heated to a temperature of 300° C. and stirred for 20minutes. After the melt mixing stage, vacuum was applied to the systemto a pressure of about 50 pascals. At those conditions the reaction wascontinued for 60 minutes. After the reaction stage the polymer wassampled from the reaction tube. The endcap level of the sampledpolycarbonate increased from 84.6% to 99.1% and the Free-OH contentdecreased from 670 to 39 ppm. The results are shown in Table 1.

COMPARATIVE EXAMPLE 21

Example 19 was repeated except that no endcapper was charged to thereactor tube. The results are shown in Table 1.

COMPARATIVE EXAMPLE 22

Example 19 was repeated except that, instead of using2-(2-carbomethoxyphenoxy)-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine0.2322 g (1.084×10⁻³ moles), DPC was charged to the reactor tube. Theresults are shown in Table 1.

COMPARATIVE EXAMPLE 23

Example 19 was repeated except that, instead of using2-(2-carbomethoxyphenoxy)-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine,0.2951 g (1.084×10⁻³ moles) methyl salicylate phenyl carbonate wascharged to the reactor tube. The results are shown in Table 1. TABLE 1Amt. Reaction Free OH Endcapper Added time content Endcap Example (moles× 10⁻³) NaOH (minutes) Mw Mn (ppm) level % 19 1.084 No 20 18287 8956 29092.4 20 2.651 Yes 60 16089 8134 39 99.1 C 21 — No 20 20992 11740 43285.1 C 22 1.084 No 20 21058 11692 347 88.1 C 23 1.084 No 20 19631 10623312 90.2

EXAMPLE 24

The process of Example 19 is essentially repeated except that2-(2-carbomethoxyphenoxy)-4-glycidoxy-6-(2,4,6-trimethylphenoxy)-1,3,5-triazineis used in place of2-(2-carbomethoxyphenoxy)-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine.Following isolation including, if desired, conversion into pellets, thepolycarbonate comprises4-glycidoxy-6-(2,4,6-trimethylphenoxy)-1,3,5-triazine end-groups.

EXAMPLE 25

The process of Example 19 is essentially repeated except that2-(2-carbomethoxyphenoxy)-4-(2-methoxy-2-methyl-1,3-dioxolanyl)methoxy-6-(2,4,6-trimethylphenoxy)-1,3,5-triazineis used in place of2-(2-carbomethoxyphenoxy)-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine.Following isolation including, if desired, conversion into pellets, thepolycarbonate comprises4-(2-methoxy-2-methyl-1,3-dioxolanyl)methoxy-6-(2,4,6-trimethylphenoxy)-1,3,5-triazineend-groups.

EXAMPLE 26

The process of Example 19 is essentially repeated except that2-allyloxy-4,6-bis(2-carbomethoxyphenoxy)-1,3,5-triazine is used inplace of2-(2-carbomethoxyphenoxy)-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine.Following isolation including, if desired, conversion into pellets, thepolycarbonate comprises 2-allyloxy-1,3,5-triazine structural units.

EXAMPLE 27

The process of Example 19 is essentially repeated except that2,4,6-tris(2-carbomethoxyphenoxy)-1,3,5-triazine is used in place of2-(2-carbomethoxyphenoxy)-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine.Following isolation including, if desired, conversion into pellets, thepolycarbonate comprises 1,3,5-triazine structural units.

EXAMPLE 28

The process of Example 19 is essentially repeated except that2-(2-carbomethoxyphenoxy)-4-(4-ethenylphenoxy)-6-(2,4,6-trimethylphenoxy)-1,3,5-triazineis used in place of2-(2-carbomethoxyphenoxy)-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine.Following isolation including, if desired, conversion into pellets, thepolycarbonate comprises4-(4-ethenylphenoxy)-6-(2,4,6-trimethylphenoxy)-1,3,5-triazineend-groups.

EXAMPLE 29

A poly(2,6-dimethyl-1,4-phenylene ether) containing at least a portionof chains containing at least one hydroxy end-group is combined in themelt with2-(2-carbomethoxyphenoxy)-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine.The mixture is mixed and heated, and the pressure is decreased to removeat least a portion of methyl salicylate. The product is isolatedincluding, if desired, conversion into pellets. The polymer comprises4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine end-groups.

EXAMPLE 30

The process of Example 29 is essentially repeated except that2-(2-carbomethoxyphenoxy)-4-glycidoxy-6-(2,4,6-trimethylphenoxy)-1,3,5-triazineis used in place of2-(2-carbomethoxyphenoxy)-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine.Following isolation including, if desired, conversion into pellets, thepolymer comprises 4-glycidoxy-6-(2,4,6-trimethylphenoxy)-1,3,5-triazineend-groups.

EXAMPLE 31

The process of Example 29 is essentially repeated except that2-(2-carbomethoxyphenoxy)-4-(2-methoxy-2-methyl-1,3-dioxolanyl)methoxy-6-(2,4,6-trimethylphenoxy)-1,3,5-triazineis used in place of2-(2-carbomethoxyphenoxy)-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine.Following isolation including, if desired, conversion into pellets, thepolymer comprises4-(2-methoxy-2-methyl-1,3-dioxolanyl)methoxy-6-(2,4,6-trimethylphenoxy)-1,3,5-triazineend-groups.

EXAMPLE 32

The process of Example 29 is essentially repeated except that2-(2-carbomethoxyphenoxy)-4-(4-ethenylphenoxy)-6-(2,4,6-trimethylphenoxy)-1,3,5-triazineis used in place of2-(2-carbomethoxyphenoxy)-4,6-bis(2,6-dimethylphenoxy)-1,3,5-triazine.Following isolation including, if desired, conversion into pellets, thepolymer comprises4-(4-ethenylphenoxy)-6-(2,4,6-trimethylphenoxy)-1,3,5-triazineend-groups.

EXAMPLE 33

A poly(2,6-dimethyl-1,4-phenylene ether) containing at least a portionof chains containing at least one hydroxy end-group and having an IVless than about 0.25 is combined in toluene solution with2-allyloxy-4,6-bis(2-carbomethoxyphenoxy)-1,3,5-triazine. The mixture issubjected to process steps comprising mixing and heating. The product isisolated using known methods. The polymer comprises2-allyloxy-1,3,5-triazine structural units.

EXAMPLE 34

The process of Example 33 is essentially repeated except that2,4,6-tris(2-carbomethoxyphenoxy)-1,3,5-triazine is used in place of2-allyloxy-4,6-bis(2-carbomethoxyphenoxy)-1,3,5-triazine, The mixture issubjected to process steps comprising mixing and heating. The product isisolated using known methods. The polymer comprises 1,3,5-triazinestructural units.

While the invention has been illustrated and described in typicalembodiments, it is not intended to be limited to the details shown,since various modifications and substitutions can be made withoutdeparting in any way from the spirit of the present invention. As such,further modifications and equivalents of the invention herein disclosedmay occur to persons skilled in the art using no more than routineexperimentation, and all such modifications and equivalents are believedto be within the spirit and scope of the invention as defined by thefollowing claims. All U.S. patents and European Patent Applicationscited herein are incorporated herein by reference.

1-6. (canceled)
 7. The process of claim 46 wherein L¹ iso-carbomethoxyphenoxy, and Z¹ and Z² are the same and are each selectedfrom the group consisting of alkyl, aryl, alkaryl, aralkyl, alkoxy,alkylamino, arylamino, aryloxy, methyl, phenyl, methoxy, ethoxy,isopropoxy, n-butoxy, iso-butoxy, t-butoxy, benzyloxy, cyclohexyloxy,methylcyclohexyloxy, nonyloxy, decyloxy, octadecyloxy, oleyloxy,phenoxy, substituted aryloxy, arylaryloxy, arylphenoxy, alkylphenoxy,2-alkylphenoxy, 3-alkylphenoxy, 4-alkylphenoxy, n-butylphenoxy,isobutylphenoxy, t-butylphenoxy, 4-t-butylphenoxy, n-pentylphenoxy,4-t-amylphenoxy, n-hexylphenoxy, cyclohexylphenoxy, phenylphenoxy,naphthylphenoxy, 4-cumylphenoxy, 4-(1,1,3,3-tetramethylbutyl)phenoxy,octylphenoxy, 4-tert-octylphenoxy, nonylphenoxy, dodecylphenoxy,octadecylphenoxy, pentadecylphenoxy, pentadecenylphenoxy,methoxyphenoxy, phenoxyphenoxy, benzyloxyphenoxy, n-hexyloxyphenoxy,2-methoxyethylphenoxy, 4-(4′-oxyphenyl)-2,2,4-trimethylchroman,2-(4′-oxyphenyl)-2,4,4-trimethylchroman,1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene,1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene,4-cyanophenoxy, dialkylphenoxy, 2,6-dialkylphenoxy, 2,6-dimethylphenoxy,2,6-di-t-butylphenoxy, 2,4-dialkylphenoxy, 2,4-di-t-butylphenoxy,2,5-dialkylphenoxy, 2,5-di-t-butylphenoxy, 2,5-dicumylphenoxy,3,5-dialkylphenoxy, 3,5-di-t-butylphenoxy, 3,5-dicumylphenoxy,2,3-dialkylphenoxy, 2,3-di-t-butylphenoxy, dimethoxyphenoxy,halophenoxy, 4-halophenoxy, 4-bromophenoxy, dihalophenoxy,dibromophenoxy, 2,6-dihalophenoxy, 2,6-dibromophenoxy,2,6-dichlorophenoxy, 2,6-(dialkoxycarbonyl)phenoxy,2,6-(dimethoxycarbonyl)phenoxy, trialkylphenoxy, 2,3,6-trialkylphenoxy,2,3,6-trimethylphenoxy, 2,4,6-trialkylphenoxy, 2,4,6-trimethylphenoxy,trihalophenoxy, tribromophenoxy, 2,4,6-trihalophenoxy,2,4,6-tribromophenoxy, and 2,4,6-trichlorophenoxy.
 8. The process ofclaim 46 wherein either Z¹, or Z², or both Z¹ and Z² are selected fromthe group consisting of vinyl, allyl, propargyloxy, olefinic groups offormula (VII; Fu¹), epoxy groups of formula (VIII; Fu²), and cyclicorthoester groups of formula (IX; Fu³):

wherein R¹ is alkyl or aryl; R² is hydrogen, alkyl, or aryl; Y¹ isnitrogen or oxygen; R³ is a C₁₋₆ alkylene radical, and R⁴ is a C₁₋₄primary or secondary alkyl radical or is an alkylene radical forming asecond 5- or 6-membered ring with C*, R⁵ is a C₁₋₄ primary or secondaryalkyl or C₆₋₁₀ aromatic radical, or R⁴ and R⁵ together with the atomsconnecting them form a 5-, 6-, or 7-membered ring; R⁶ is hydrogen or aC₁₋₄ primary or secondary alkyl; m is zero or one, and n is from 1 to2m; and x is zero when R⁴ and C* form a ring and is otherwise one. 9-13.(canceled)
 14. The process of claim 8 wherein L¹ iso-carbomethoxyphenoxy; Z¹ is selected from the group consisting ofalkyl, aryl, alkaryl, aralkyl, alkoxy, alkylamino, arylamino, aryloxy,methyl, phenyl, methoxy, ethoxy, isopropoxy, n-butoxy, iso-butoxy,t-butoxy, benzyloxy, cyclohexyloxy, methylcyclohexyloxy, nonyloxy,decyloxy, octadecyloxy, oleyloxy, phenoxy, substituted aryloxy,arylaryloxy, arylphenoxy, alkylphenoxy, 2-alkylphenoxy, 3-alkylphenoxy,4-alkylphenoxy, n-butylphenoxy, isobutylphenoxy, t-butylphenoxy,4-t-butylphenoxy, n-pentylphenoxy, 4-t-amylphenoxy, n-hexylphenoxy,cyclohexylphenoxy, phenylphenoxy, naphthylphenoxy, 4-cumylphenoxy,4-(1,1,3,3-tetramethylbutyl)phenoxy, octylphenoxy, 4-tert-octylphenoxy,nonylphenoxy, dodecylphenoxy, octadecylphenoxy, pentadecylphenoxy,pentadecenylphenoxy, methoxyphenoxy, phenoxyphenoxy, benzyloxyphenoxy,n-hexyloxyphenoxy, 2-methoxyethylphenoxy,4-(4′-oxyphenyl)-2,2,4-trimethylchroman,2-(4′-oxyphenyl)-2,4,4-trimethylchroman,1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene,1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene,4-cyanophenoxy, dialkylphenoxy, 2,6-dialkylphenoxy, 2,6-dimethylphenoxy,2,6-di-t-butylphenoxy, 2,4-dialkylphenoxy, 2,4-di-t-butylphenoxy,2,5-dialkylphenoxy, 2,5-di-t-butylphenoxy, 2,5-dicumylphenoxy,3,5-dialkylphenoxy, 3,5-di-t-butylphenoxy, 3,5-dicumylphenoxy,2,3-dialkylphenoxy, 2,3-di-t-butylphenoxy, dimethoxyphenoxy,halophenoxy, 4-halophenoxy, 4-bromophenoxy, dihalophenoxy,dibromophenoxy, 2,6-dihalophenoxy, 2,6-dibromophenoxy,2,6-dichlorophenoxy, 2,6-(dialkoxycarbonyl)phenoxy,2,6-(dimethoxycarbonyl)phenoxy, trialkylphenoxy, 2,3,6-trialkylphenoxy,2,3,6-trimethylphenoxy, 2,4,6-trialkylphenoxy, 2,4,6-trimethylphenoxy,trihalophenoxy, tribromophenoxy, 2,4,6-trihalophenoxy,2,4,6-tribromophenoxy, and 2,4,6-trichlorophenoxy; and Z² is selectedfrom the group consisting of vinyl, allyl, allyloxy, 2-allylphenoxy,4-allylphenoxy, 4-ethenylphenoxy, cinnamyloxy, 4-allyl-2-methoxyphenoxy,propargyloxy, glycidoxy, and4-oxymethyl-2-methoxy-2-methyl-1,3-dioxolane.
 15. (canceled)
 16. Theprocess of claim 8 wherein L¹ is o-carbomethoxyphenoxy; and Z¹ and Z²are the same and are selected from the group consisting of vinyl, allyl,allyloxy, 2-allylphenoxy, 4-allylphenoxy, 4-ethenylphenoxy, cinnamyloxy,4-allyl-2-methoxyphenoxy, propargyloxy, glycidoxy, and4-oxymethyl-2-methoxy-2-methyl-1,3-dioxolane. 17-45. (canceled)
 46. Aprocess for capping nucleophilic groups in a polymer which comprisescombining and reacting the polymer with a triazine-comprising cappingagent of formula (I):

wherein L¹ is an aryloxy group comprising at least one electronwithdrawing group ortho, meta, or para to the linkage between thearyloxy group and the triazine ring, and Z¹ and Z² are eachindependently groups which are essentially inert to reaction with anucleophilic group on a polymer or monomer, or which react with anucleophilic group on a polymer or monomer at a slower rate than thegroup, L¹, and wherein the polymer does not comprise triazine-containingmoiety as a structural unit in the polymer chain other than at aterminal site. 47-75. (canceled)
 76. A process for capping terminalhydroxy groups in a polycarbonate which comprises combining and reactingthe polymer with a triazine-comprising capping agent of the formula (I):

wherein L¹ is o-carbomethoxyphenoxy, and Z¹ and Z² are eachindependently selected from the group consisting of alkyl, aryl,alkaryl, aralkyl, alkoxy, alkylamino, arylamino, aryloxy, methyl,phenyl, methoxy, ethoxy, isopropoxy, n-butoxy, iso-butoxy, t-butoxy,benzyloxy, cyclohexyloxy, methylcyclohexyloxy, nonyloxy, decyloxy,octadecyloxy, oleyloxy, phenoxy, substituted aryloxy, arylaryloxy,arylphenoxy, alkylphenoxy, 2-alkylphenoxy, 3-alkylphenoxy,4-alkylphenoxy, n-butylphenoxy, isobutylphenoxy, t-butylphenoxy,4-t-butylphenoxy, n-pentylphenoxy, 4-t-amylphenoxy, n-hexylphenoxy,cyclohexylphenoxy, phenylphenoxy, naphthylphenoxy, 4-cumylphenoxy,4-(1,1,3,3-tetramethylbutyl)phenoxy, octylphenoxy, 4-tert-octylphenoxy,nonylphenoxy, dodecylphenoxy, octadecylphenoxy, pentadecylphenoxy,pentadecenylphenoxy, methoxyphenoxy, phenoxyphenoxy, benzyloxyphenoxy,n-hexyloxyphenoxy, 2-methoxyethylphenoxy,4-(4′-oxyphenyl)-2,2,4-trimethylchroman,2-(4′-oxyphenyl)-2,4,4-trimethylchroman,1-(1-methyl-1-phenylethyl)-4-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene,1,3-bis(1-methyl-1-phenylethyl)-5-(1-methyl-1-(4′-oxyphenyl)ethyl)-benzene,4-cyanophenoxy, dialkylphenoxy, 2,6-dialkylphenoxy, 2,6-dimethylphenoxy,2,6-di-t-butylphenoxy, 2,4-dialkylphenoxy, 2,4-di-t-butylphenoxy,2,5-dialkylphenoxy, 2,5-di-t-butylphenoxy, 2,5-dicumylphenoxy,3,5-dialkylphenoxy, 3,5-di-t-butylphenoxy, 3,5-dicumylphenoxy,2,3-dialkylphenoxy, 2,3-di-t-butylphenoxy, dimethoxyphenoxy,halophenoxy, 4-halophenoxy, 4-bromophenoxy, dihalophenoxy,dibromophenoxy, 2,6-dihalophenoxy, 2,6-dibromophenoxy,2,6-dichlorophenoxy, 2,6-(dialkoxycarbonyl)phenoxy,2,6-(dimethoxycarbonyl)phenoxy, trialkylphenoxy, 2,3,6-trialkylphenoxy,2,3,6-trimethylphenoxy, 2,4,6-trialkylphenoxy, 2,4,6-trimethylphenoxy,trihalophenoxy, tribromophenoxy, 2,4,6-trihalophenoxy,2,4,6-tribromophenoxy, 2,4,6-trichlorophenoxy, vinyl, allyl, allyloxy,2-allylphenoxy, 4-allylphenoxy, 4-ethenylphenoxy, cinnamyloxy,4-allyl-2-methoxyphenoxy, propargyloxy, glycidoxy, and4-oxymethyl-2-methoxy-2-methyl-1,3-dioxolane, and wherein thepolycarbonate does not comprise triazine-containing moiety as astructural unit in the polymer chain other than at a terminal site. 77.The process of claim 76 wherein the polycarbonate is derived from a meltreaction process with reactants comprising bisphenol A anddiphenylcarbonate. 78-99. (canceled)
 100. A process for cappingnucleophilic groups in a polymer which comprises combining and reactingthe polymer with a triazing moiety, said moiety comprising at least onevinyl, allyl, or propargyloxy group or olefinic group of formula (VII;Fu¹):

wherein R¹ is alkyl or aryl; and R² is hydrogen, alkyl or aryl, whereinthe polymer is a poly (phenylene ether) comprising 2-6-dimethylphenylene structural units,